Method for hydrosilylation of aliphatically unsaturated alkoxysilanes and hydrogen terminated organosiloxane oligomers to prepare alkoxysilyl terminated polymers useful for functionalizing polyorganosiloxanes using an iridium catalyst

ABSTRACT

A method for preparing a product includes combining starting materials including A) a siloxane oligomer having silicon bonded hydrogen atoms, B) an alkoxysilane having at least one aliphatically unsaturated group capable of undergoing hydrosilylation reaction and C) an iridium complex catalyst. The method can be used to produce a compound of formula (I). This compound can be used in a hydrosilylation reaction with a vinyl-functional polyorganosiloxane. The resulting product includes an ethyltrimethoxysilyl functional polyorganosiloxane useful in condensation reaction curable sealant compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/524,637 filed Jun. 26, 2017 under 35 U.S.C. § 119(e). U.S. Provisional Patent Application No. 62/524,637 is herebyincorporated by reference.

BACKGROUND

In the reaction scheme shown below, hydrosilylation reaction ofvinyltrimethoxysilane with 1,1,3,3-tetramethyldisiloxane using aplatinum catalyst yields a mixture including the α-adduct branchedisomer and β-adduct linear isomer as reaction products.

However, this method suffers from the drawback that selectivity resultsin a 65/35 mole ratio of β-adduct/α-adduct. In addition, without promptremoval or deactivation of the Pt catalyst, “over hydrosilylation” willoccur, leading to side products in which both hydrogen atoms on thehydrogen terminated organosiloxane oligomer have reacted with avinyltrimethoxysilane molecule, i.e., αα adduct, αβ adduct, βα adduct,and/or ββ adduct. One method for minimizing the formation of these sideproducts is to use a molar excess of 1,1,3,3-tetramethyldisiloxane.However, this method suffers from the drawback of process inefficiencyand the need to recover relatively large amounts of unreacted1,1,3,3-tetramethyldisiloxane.

There is an industry need to provide one or more of the followingbenefits: 1) minimize the formation of side products due to overhydrosilylation; 2) produce the beta-adduct with high selectivity andhigh yield; and 3) produce the beta-adduct stable in the presence ofcatalyst.

BRIEF SUMMARY OF THE INVENTION

A method for selectively preparing a product comprising analkoxy-functional organohydrogensiloxane oligomer comprises:

1) reacting starting materials comprising:

(A) a polyorganohydrogensiloxane oligomer of unit formula (I):

(HR¹ ₂SiO_(1/2))_(e)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(SiO_(4/2))_(k)

where subscripts e, f, g, h, i, j, and k have values such that 5≥e≥0,5≥f≥0, 10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or1, with the proviso that a quantity (e+g+j)≥2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently a monovalenthydrocarbon group of 1 to 18 carbon or a monovalent halogenatedhydrocarbon group of 1 to 18 carbon atoms;

(B) an aliphatically unsaturated alkoxysilane of formula (II):

where R¹ is as described above, each R² is independently analiphatically unsaturated monovalent hydrocarbon group of 2 to 18 carbonatoms, each R³ is independently a monovalent hydrocarbon group of 1 to18 carbon atoms, subscript c is 0 or 1; and

(C) an iridium complex of formula [Ir(R⁵)_(x)(R⁶)_(y)]_(z), wheresubscript x is 1 or 2, R⁵ is a 1,5-cyclooctadiene ligand or a2,5-norbornadiene ligand, subscript y is 0, 1 or 2, R⁶ is a ligand thatcan be activated at a temperature less than a boiling point of theorganohydrogensiloxane oligomer, and subscript z is 1 or 2, therebypreparing the reaction product comprising the alkoxy-functionalorganohydrogensiloxane oligomer; and optionally 2) isolating thealkoxy-functional organohydrogensiloxane oligomer prepared in step 1).

In step 1), starting material (C) and starting material (B) may becombined and metered into starting material (A).

The alkoxy-functional organohydrogensiloxane oligomer has unit formula(III):

where R¹, R³, and subscripts c, f, h, i, and k are as described above,subscript b is 0 to 2, m>0, and a quantity (m+n+o+p)=(e+g+j), and each Dis independently a divalent hydrocarbon group of 2 to 18 carbon atoms,with the proviso that >90 mol % of all D groups produced in step 1) arelinear.

The alkoxy-functional organohydrogensiloxane oligomer is useful in amethod for preparing a poly-alkoxy functional polyorganosiloxane. Themethod for preparing the poly-alkoxy functional polyorganosiloxanecomprises:

(1) reacting starting materials comprising:

(a) an alkoxy-functional organohydrogensiloxane oligomer describedabove,

(b) a polyorganosiloxane having, per molecule, an average of at leasttwo aliphatically unsaturated monovalent hydrocarbon groups; and

(c) a hydrosilylation reaction catalyst.

DETAILED DESCRIPTION OF THE INVENTION

The method for selectively preparing a product comprising analkoxy-functional organohydrogensiloxane oligomer comprises:

1) reacting starting materials comprising:

(A) a polyorganohydrogensiloxane oligomer of unit formula (I):

(HR¹ ₂SiO_(1/2))_(e)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(SiO_(4/2))_(k)

where subscripts e, f, g, h, i, j, and k have values such that 5≥e≥0,5≥f≥0, 10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or1, with the proviso that a quantity (e+g+j)≥2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently a monovalenthydrocarbon group of 1 to 18 carbon or a monovalent halogenatedhydrocarbon group of 1 to 18 carbon atoms;

(B) an aliphatically unsaturated alkoxysilane of formula (II):

where each R² is independently an aliphatically unsaturated monovalenthydrocarbon group of 2 to 18 carbon atoms, each R³ is independently amonovalent hydrocarbon group of 1 to 18 carbon atoms, subscript c is 0or 1; and

(C) an iridium complex of formula [Ir(R⁵)_(x)(R⁶)_(y)]_(z), wheresubscript x is 1 or 2, R⁵ is a 1,5-cyclooctadiene ligand or a2,5-norbornadiene ligand, subscript y is 0, 1 or 2, R⁶ is a ligand thatcan be activated at a temperature less than a boiling point of theorganohydrogensiloxane oligomer, and subscript z is 1 or 2, therebypreparing the reaction product comprising the alkoxy-functionalorganohydrogensiloxane oligomer; and optionally 2) isolating thealkoxy-functional organohydrogensiloxane oligomer prepared in step 1).

Ingredient (A) useful in the method described above is apolyorganohydrogensiloxane oligomer of unit formula (III):

(HR¹ ₂SiO_(1/2))_(e)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(SiO_(4/2))_(k)

where subscripts e, f, g, h, i, j, and k have values such that 5≥e≥0,5≥f≥0, 10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or1, with the proviso that a quantity (e+g+j)≥2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently a monovalenthydrocarbon group of 1 to 18 carbon or a monovalent halogenatedhydrocarbon group of 1 to 18 carbon atoms. Alternatively, monovalenthydrocarbon groups for R¹ have 1 to 12 carbon atoms, and alternatively 1to 10 carbon atoms.

Suitable monovalent hydrocarbon groups for R¹ include, but are notlimited to, an alkyl group of 1 to 6 carbon atoms and an aryl group of 6to 10 carbon atoms. Suitable alkyl groups for R¹ are exemplified by, butnot limited to, methyl, ethyl, propyl (e.g., iso-propyl and/orn-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/orsec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl),hexyl, as well as branched saturated hydrocarbon groups of 6 carbonatoms. Suitable aryl groups for R¹ are exemplified by, but not limitedto, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl.Suitable monovalent halogenated hydrocarbon groups for R¹ include, butare not limited to, a halogenated alkyl group of 1 to 6 carbon atoms, ora halogenated aryl group of 6 to 10 carbon atoms. Suitable halogenatedalkyl groups for R¹ are exemplified by, but not limited to, the alkylgroups described above where one or more hydrogen atoms is replaced witha halogen atom, such as F or Cl. For example, fluoromethyl,2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl,4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl,6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl,2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl,and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl,2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples ofsuitable halogenated alkyl groups. Suitable halogenated aryl groups forR¹ are exemplified by, but not limited to, the aryl groups describedabove where one or more hydrogen atoms is replaced with a halogen atom,such as F or Cl. For example, chlorobenzyl and fluorobenzyl are suitablehalogenated aryl groups. Alternatively, each R¹ is independently methyl,ethyl or propyl. Each instance of R¹ may be the same or different.Alternatively, each R¹ is a methyl group. Examples of suitablehydridosilanes include trimethylsilane and trimethoxysilane.

In an alternative embodiment, ingredient (A) is an α,γ-hydrogenterminated organohydrogensiloxane oligomer of formula (IV):

where each R¹ is independently an alkyl group of 1 to 6 carbon atoms, anaryl group of 6 to 10 carbon atoms, a halogenated alkyl group of 1 to 6carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms; andsubscript a is an integer up to 20. Alternatively, subscript a is 0 to20, alternatively subscript a is 0 to 10; alternatively subscript a is 0to 5; and alternatively subscript a is 0 or 1. Alternatively, subscripta may be 2 to 10; alternatively subscript a is 2 to 5. Examples ofsuitable organohydrogensiloxane oligomers include1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3-tetramethyldisiloxane,1,1,3,3,5,5-hexaethyltrisiloxane, and 1,1,3,3-tetraethyldisiloxane.Alternatively, ingredient (A) may be 1,1,3,3-tetramethyldisiloxane.

When the organohydrogensiloxane oligomer of formula (IV) is used in themethod, the product comprises an alkoxy-functionalorganohydrogensiloxane oligomer produced of formula (V):

where R¹ and subscripts a and c are as described above, D is a divalenthydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol% of D are linear divalent hydrocarbon groups.

In an alternative embodiment, ingredient (A) the organohydrogensiloxaneoligomer has unit formula (VI): (HR¹ ₂SiO_(1/2))₃(R¹₂SiO_(2/2))_(q)(R¹SiO_(3/2)), where subscript q is 0 to 3. Thepolyorganohydrogensiloxane oligomer of this unit formula may haveformula (VII):

where R¹ is as described above. Examples of such organohydrogensiloxaneoligomers include siloxanes of formula (Me₂HSiO_(1/2))₃(PrSiO_(3/2)),where Me represents a methyl group and Pr represents a propyl group.

When the organohydrogensiloxane oligomer used for ingredient A) in themethod described above has unit formula (VI) or (VII), the product maycomprise an alkoxy-functional organohydrogensiloxane oligomer of formula(VIIIa), formula (VIIIb), or both, where formula (VIIIa) is:

and formula (VIIIb) is:

where R¹ and subscript c are as described above, each D is independentlya divalent hydrocarbon group of 2 to 18 carbon atoms, with the provisothat >90 mol % of D are linear divalent hydrocarbon groups.

In an alternative embodiment of the invention, ingredient (A) theorganohydrogensiloxane oligomer may have unit formula (IX): (HR¹₂SiO_(1/2))₂(R¹ ₂SiO_(2/2))_(q)(HR¹SiO_(2/2))_(r), where R¹ is asdescribed above, subscript q is 0 to 3, and subscript r is 0 to 3. Inthis embodiment, the organohydrogensiloxane oligomer may have formula(X):

where R¹ is as described above. Examples of such organohydrogensiloxaneoligomers include 1,1,3,5,5-pentamethyltrisiloxane. In this embodiment,the product comprises an alkoxy-functional organohydrogensiloxaneoligomer of formula (XI), formula (XII), or a combination thereof, whereformula (XI) is

and formula (XII) is

where R¹ and subscript c are as described above.

In an alternative embodiment ingredient (A) the organohydrogensiloxaneoligomer is cyclic. The cyclic organohydrogensiloxane oligomer may haveunit formula: (R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(s), where R¹ is asdescribed above, subscript s≥3, and subscript v≥0. Alternatively,subscript s may be 3 to 14; alternatively 3 to 9, alternatively 3 to 6,alternatively 3 to 5, and alternatively 4. Alternatively, subscript vmay be 0 to 14; alternatively 0 to 9, alternatively 0 to 6,alternatively 0 to 5, and alternatively 0. When this cyclicorganohydrogensiloxane oligomer is used as ingredient (A), then theproduct may comprise an alkoxy-functional organohydrogensiloxaneoligomer of unit formula (XIII):

(R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(t)

where R, R¹, D, and subscripts c and v are as described above, subscriptt is 0 or more, subscript u is 1 or more, and a quantity (t+u)=s.

Ingredient (B) useful in the method described above is an aliphaticallyunsaturated alkoxysilane of formula (XIV): R¹ _(d)R²Si(OR³)_((3−d)),where each R¹ is independently a monovalent hydrocarbon group or amonovalent halogenated hydrocarbon group (as described above), each R²is independently an aliphatically unsaturated hydrocarbon group, each R³is independently a monovalent hydrocarbon group, subscript d is 0 or 1.The aliphatically unsaturated hydrocarbon group for R² may be an alkenylgroup or an alkynyl group. Suitable alkenyl groups include vinyl, allyl,propenyl, butenyl and hexenyl; alternatively vinyl, allyl or hexenyl;and alternatively vinyl. The monovalent hydrocarbon group for R³ may bea monovalent hydrocarbon group as described above for R¹.

Ingredient (B) may comprise an aliphatically unsaturated alkoxysilaneexemplified by a dialkoxysilane, such as a dialkenyldialkoxysilane; atrialkoxysilane, such as an alkenyltrialkoxysilane; or a combinationthereof. Examples of suitable aliphatically unsaturated alkoxysilanesinclude vinyltrimethoxysilane, allyltriethoxysilane,allyltrimethoxysilane, vinyltriethoxysilane, hexenyltrimethoxysilane,vinylmethyldimethoxysilane, hexenylmethyldimethoxysilane,hexenyltriethoxysilane, and a combination thereof, and alternativelyvinyltrimethoxysilane.

Ingredient (A) and ingredient (B) are present in relative molar amountsof ingredient (A):ingredient (B) of 1:1 to >1:1, alternatively greaterthan or equal to 1, i.e., (A):(B) ratio≥1:1. Alternatively, (A):(B)ratio may range from 5:1 to 1:1, alternatively 2:1 to 1:1; andalternatively 1.5:1 to 1:1. Without wishing to be bound by theory, it isthought that a molar excess of ingredient (A) relative to ingredient (B)may favorably affect yield in the product.

Ingredient (C) useful in the method and composition described herein isan iridium complex. The iridium complex has formula (XV):[Ir(R⁵)_(x)(R⁶)_(y)]_(z), where subscript x is 1 or 2, R⁵ is a1,5-cyclooctadiene ligand or a 2,5-norbornadiene ligand, subscript y is0 to 2, alternatively 0 or 1, R⁶ is a ligand that can be activated, andsubscript z is 1 or 2. Alternatively, subscript z=2. Activating withrespect to R⁶ may be performed by any convenient means, such as heatingat a temperature less than the boiling point of theorganohydrogensiloxane oligomer, adding a silver salt, or byphotochemical or electrochemical means in step (1) of the methoddescribed herein. R⁶ may be an anionic ligand. Examples of ligandssuitable for R⁶ include a halogen atom, a beta-ketoester ligand, ahalogenated beta-ketoester ligand, an alkoxy ligand, a cyanoalkylligand, an aryl ligand, and a heteroaryl ligand. Examples of suitablehalogen atoms include bromine (Br), chlorine (Cl) and iodine (I).Alternatively, the halogen atom may be Cl. Examples of beta-ketoesterligands include acetyl acetonate (acac). Examples of halogenatedbeta-ketoesters include hexafluoro acetylacetonate (hfacac). Examples ofalkoxy ligands include methoxy, ethoxy, and propoxy. Alternatively thealkoxy ligand may be methoxy. Examples of suitable cyanoalkyl ligandsinclude CH₃CN, acetonitrile, and tetrahydrofuran (THF). Examples ofsuitable aryl ligands include phenyl, benzyl, or indenyl. Examples ofsuitable heteroaryl ligands include pyridine.

Examples suitable catalysts for ingredient (C) include, but are notlimited to [Ir(I)CODCl-dimer, Ir(I)CODacac, Ir(I)COD₂BARF,Ir(I)COD(OMe)-dimer, Ir(I)COD(hfacac), Ir(I)COD(CH₃CN)₂,Ir(I)COD(pyridine), Ir(I)COD(indenyl), and mixtures thereof; wherein CODrepresents a 1,5-cyclooctadiene group, BARF representstetrakis(3,5-bis(trifluoromethyl)phenyl)borate, acac represents acetylacetonate, and hfacac represents hexafluoro acetylacetonate.

The amount of ingredient (C) used in step (1) of the method describedabove depends on various factors including the specificorganohydrogensiloxane oligomer selected for ingredient (A), thespecific alkoxysilane selected for ingredient (B), and the temperatureto which the mixture can be heated without boiling away theorganohydrogensiloxane oligomer selected for ingredient (A). However,the amount of ingredient (C) may be sufficient to provide a molar amountof iridium metal of 1 parts per million (ppm) to 100 ppm, alternatively5 ppm to 80 ppm, alternatively 5 ppm to 20 ppm based on combined weightsof ingredients (A) and (B). The method may optionally further comprisedeactivation or removal of the catalyst. However, with appropriatecatalyst loading, the step of deactivation or removal of the catalystmay be omitted.

The method described herein may be performed at 1 atmosphere of pressureor higher. Alternatively, the method may be performed at 1 atmosphere to1.5 atmosphere. Step 1) may be performed at 0° C. to 150° C.,alternatively 50° C. to 150° C., alternatively 60° C. to 150° C., andalternatively 50° C. to 100° C. The temperature for heating in step 1)depends on various factors including the pressure selected, however,heating may be performed at least 70° C. to ensure the reaction proceedsquickly enough to be practical. The upper limit for temperature duringheating is not critical and depends on the ingredients selected, i.e.,the upper limit should be such that the ingredients do not vaporize outof the reactor selected for performing the method. Alternatively,heating may be from 70° C. to 150° C., alternatively 70° C. to 100° C.

Step (1) of the method described above produces a product comprising analkoxy-functional organohydrogensiloxane oligomer. The alkoxy-functionalorganohydrogensiloxane oligomer has unit formula (XVI):

whereR¹, R³, and subscripts c, f, h, i, and k are as described above,subscript b is 0 to 2, subscript m>0, and subscripts m, n, o, and p havevalues such that a quantity (m+n+o+p)=(e+g+j), and each D isindependently a divalent hydrocarbon group of 2 to 18 carbon atoms, withthe proviso that >90 mol % of all D groups produced in step 1) arelinear. Subscripts e, g, and j are as described above in formula (I).The method described herein provides the benefit that thisalkoxy-functional organohydrogensiloxane oligomer is produced with highselectivity to the β-adduct compound, i.e., where D is linear, witheither none or lower amounts of the corresponding α-adduct compound thanexisting methods using other catalysts.

The ingredients in step 1) of the method described above form a mixture,which may be homogeneous or heterogeneous. Alternatively, ingredientscomprising (B) and (C) may be combined, e.g., by mixing and theresulting mixture comprising ingredients (B) and (C) may be graduallyadded into ingredients comprising (A). One or more additionalingredients, i.e., in addition to ingredients (A), (B), and (C)described above, may optionally be used in the method and compositiondescribed herein. The additional ingredient, when present, may be (D) asolvent or (E) a stabilizer, or both (D) and (E).

Ingredient (D) is a solvent that may be added to the mixture used instep 1) of the method described herein. One or more of ingredients (A),(B), and/or (C) may be provided in a solvent. For example, ingredient(C) may be dissolved in a solvent that is added to a mixture ofingredients (A) and (B) in step 1). Alternatively, ingredients (B) and(C) may be combined with a solvent, and the resulting solution graduallymetered into a vessel containing ingredient (A), optionally mixed withsolvent. The solvent for ingredients (B) and (C) and the solvent foringredient (A) may be the same or different. The solvent may facilitatecontacting of reactants and catalyst, flow of the mixture and/orintroduction of certain ingredients, such as the catalyst. Solvents usedherein are those that help fluidize the ingredients of the mixture butessentially do not react with any of these ingredients. Solvents may beselected based on solubility the ingredients in the mixture andvolatility. The solubility refers to the solvent being sufficient todissolve ingredients of the mixture. Volatility refers to vapor pressureof the solvent. If the solvent is too volatile (having too high vaporpressure) the solvent may not remain in solution during heating.However, if the solvent is not volatile enough (too low vapor pressure)the solvent may be difficult to remove from the product or isolate fromthe alkoxy-functional organohydrogensiloxane oligomer.

The solvent may be an organic solvent. The organic solvent can be anaromatic hydrocarbon such as benzene, toluene, or xylene, or acombination thereof. Ingredient (D) may be one solvent. Alternatively,ingredient (D) may comprise two or more different solvents.

The amount of solvent can depend on various factors including thespecific solvent selected and the amount and type of other ingredientsselected for the mixture. However, the amount of solvent may range from0% to 99%, or when present, 1% to 99%, and alternatively 2% to 50%,based on the weight of the mixture.

Starting material (E), the stabilizer may be an oxidant, a diene, or apolyene. Step 1) may optionally be performed in the presence of anoxidant, such as oxygen gas (O₂), an organic oxidant such as a quinone,or an inorganic oxidant such as an oxide (as described, for example, inDE102005030581). Alternatively, the stabilizer may be a diene or polyeneadded in excess to further stabilize the Ir catalyst to allow betteroverall performance (as described, for example in WO 2008107332 A1,EP1156052 B1, EP1633761 B1, EP1201671 B1, DE10232663 C1).

The method may optionally further comprise one or more additional steps.The method may further comprise a step of: recovering a fractioncontaining the alkoxy-functional organohydrogensiloxane oligomer fromthe product. Because the alkoxy-functional organohydrogensiloxaneoligomer may comprise a β-adduct compound (i.e., where D is linear) anda corresponding α-adduct compound (i.e., where D is not linear) aredifficult and/or costly to separate from one another, a fractioncomprising both β-adduct compound and α-adduct compound may be recoveredfrom the product after step 1) described above. It is desirable thatthis fraction contain >90% β-adduct compound, alternatively >90% to 100%β-adduct compound, alternatively 92% to 100%, alternatively >90% to<100%, alternatively 92% to <100%, and alternatively 95% to <100%β-adduct compound, based on the combined amounts of β-adduct compoundand α-adduct compound in the fraction. Recovering this fraction may beperformed by any convenient means, such as stripping or distillation,with heating or under vacuum, or a combination thereof.

The fraction described above comprising the β-adduct compoundalkoxy-functional organohydrogensiloxane oligomer above is useful forfunctionalization of polyorganosiloxanes, including oligomers and longerchain polymers, containing aliphatically unsaturated functionality. Forexample, a hydrosilylation reaction of the SiH group in thealkoxy-functional organohydrogensiloxane oligomer of formula (X) with analiphatically unsaturated group bonded to silicon in apolyorganosiloxane (such as a polydiorganosiloxane having aliphaticallyunsaturated terminal groups) can produce an alkoxy-functionalpolyorganosiloxane. The polyorganosiloxane having aliphaticallyunsaturated terminal groups may have unit formula (XVII):(R⁷R₈SiO_(1/2))_(e)(R⁷R₈SiO_(2/2))_(f)(R⁷SiO_(3/2))_(g)(SiO_(4/2))_(h),where each R⁷ is independently a hydrogen atom, an alkyl group, an arylgroup, a halogenated alkyl group, or a halogenated aryl group (such asthose described above for R¹), and each R⁸ is independently analiphatically unsaturated hydrocarbon group such as an alkenyl groupexemplified by alkenyl groups such as vinyl, allyl, butenyl, andhexenyl; and alkynyl groups such as ethynyl and propynyl. Subscript e isan integer of 0 or more, subscript f is an integer of 0 or more,subscript g is an integer of 0 or more, and subscript h is an integer of0 or more, with the proviso that a quantity (f+g)≥1. Alternatively, thepolyorganosiloxane may be a polydiorganosiloxane. Thepolydiorganosiloxane having aliphatically unsaturated terminal groupsmay have formula (XVIII):

R⁷ ₂R₈SiO(R⁷ ₂SiO)_(d)SiR⁷ ₂R₈.

In formula (XVIII), R⁷ and R⁸ are as described above. Subscript d may be0 or a positive number. Alternatively, each R⁷ may be an alkyl group oran aryl group as described above for R¹. Alternatively, subscript d hasan average value of at least 2. Alternatively subscript d may have avalue ranging from 2 to 2000.

The compound of formula (XIX) may comprise a polydiorganosiloxane suchas i) dimethylvinylsiloxy-terminated polydimethylsiloxane, ii)dimethylvinylsiloxy-terminatedpoly(dimethylsiloxane/methylphenylsiloxane), iii)dimethylvinylsiloxy-terminated poly(dimethylsiloxane/diphenylsiloxane),iv) phenyl, methyl, vinyl-siloxy-terminated polydimethylsiloxane, or v)dimethylhexenylsiloxy-terminated polydimethylsiloxane.

The alkoxy-functional polyorganosiloxane may be produced by combiningthe product or fraction including the β-adduct compoundalkoxy-functional organohydrogensiloxane oligomer with apolydiorganosiloxane of formula (XIX) as described above.

The hydrosilylation reaction to prepare the alkoxy-functionalpolyorganosiloxane may be performed by a method comprising:

combining starting materials comprising(a) the product (or fraction) comprising the β-adduct compoundalkoxy-functional organohydrogensiloxane oligomer as described above,(b) the polyorganosiloxane having at least one aliphatically unsaturatedsilicon bonded group per molecule as described above, and(c) a hydrosilylation catalyst other than the iridium complex describedabove. Suitable catalysts for catalyzing hydrosilylation reaction areknown in the art and are commercially available. Such hydrosilylationcatalysts can be a platinum group metal, such as platinum.Alternatively, the hydrosilylation catalyst may be a compound of such ametal, for example, chloroplatinic acid, chloroplatinic acidhexahydrate, platinum dichloride, and complexes of said compounds withlow molecular weight organopolysiloxanes or platinum compoundsmicroencapsulated in a matrix or core/shell type structure. Complexes ofplatinum with low molecular weight organopolysiloxanes include1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum.These complexes may be microencapsulated in a resin matrix. Exemplaryhydrosilylation catalysts are described in U.S. Pat. Nos. 3,159,601;3,220,972; 3,296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668;4,784,879; 5,036,117; and 5,175,325 and EP 0 347 895 B.Microencapsulated hydrosilylation catalysts and methods of preparingthem are known in the art, as exemplified in U.S. Pat. Nos. 4,766,176and 5,017,654. Combining the starting materials may be performed atelevated temperature, such as heating at 50° C. to 250° C.

The polyalkoxy-functional polyorganosiloxanes produced by thehydrosilylation of described above may have formula: (XX): R⁷ ₂R¹¹SiO(R⁷₂SiO)_(d)SiR⁷ ₂R¹¹, where R⁷ and subscript d are as described above, andeach R¹¹ is polyalkoxyfunctional group, with the proviso that >90 mol %of R¹¹ are β-adduct. Alternatively, in formula (XIII), >90 mol % to 100mol % of R¹¹ are β-adduct groups. Alternatively, in formula (XIII), 92%to <100% % of R¹¹ are β-adduct groups.

For example, when (b) the polyorganosiloxane having aliphaticallyunsaturated terminal groups is a polydiorganosiloxane of formula (XIV):

where subscript n is 1 to 2,000; the poly-alkoxy functionalpolyorganosiloxane may have formula (XXI):

where each D¹ is independently a divalent hydrocarbon group; where R¹,R², D and subscript c are as described above.

Alternatively, the poly-alkoxy functional polyorganosiloxane may haveformula (XXII):

where each D¹ is independently a divalent hydrocarbon group; where R¹,R², D and subscript c are as described above.

The poly-alkoxy functional polyorganosiloxanes, such aspolyalkoxy-functional polydimethylsiloxanes, prepared as described abovecan be used in any application that utilizes reactivity of the alkoxygroups.

For example, the poly-alkoxy functional polyorganosiloxane prepared asdescribed above is useful in condensation reaction curable compositions,such as sealant compositions. Suitable condensation reaction curablecompositions can be prepared by mixing starting materials comprising:

(i) the poly-alkoxy functional polyorganosiloxane prepared as describedabove, and

(ii) condensation reaction catalyst. Without wishing to be bound bytheory, it thought that a condensation reaction curable compositionincluding (i) the poly-alkoxy functional polyorganosiloxane will curefaster than a similar condensation reaction curable compositioncontaining a different poly-alkoxy functional polyorganosiloxane(prepared using a conventional endblocker having higher branched isomercontent).

Starting material (ii) is a condensation reaction catalyst. Suitablecondensation reaction catalysts include tin catalysts and titaniumcatalysts. Suitable tin catalysts include organotin compounds where thevalence of the tin is either +4 or +2, i.e., Tin (IV) compounds or Tin(II) compounds. Examples of tin (IV) compounds include stannic salts ofcarboxylic acids such as dibutyl tin dilaurate, dimethyl tin dilaurate,di-(n-butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tinmaleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide,carbomethoxyphenyl tin tris-uberate, dibutyl tin dioctanoate, dibutyltin diformate, isobutyl tin triceroate, dimethyl tin dibutyrate,dimethyl tin di-neodeconoate, dibutyl tin di-neodeconoate, triethyl tintartrate, dibutyl tin dibenzoate, butyltintri-2-ethylhexanoate, dioctyltin diacetate, tin octylate, tin oleate, tin butyrate, tin naphthenate,dimethyl tin dichloride, a combination thereof, and/or a partialhydrolysis product thereof. Tin (IV) compounds are known in the art andare commercially available, such as Metatin® 740 and Fascat® 4202 fromAcima Specialty Chemicals of Switzerland, Europe, which is a businessunit of The Dow Chemical Company. Examples of tin (II) compounds includetin (II) salts of organic carboxylic acids such as tin (II) diacetate,tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate,stannous salts of carboxylic acids such as stannous octoate, stannousoleate, stannous acetate, stannous laurate, stannous stearate, stannousnaphthanate, stannous hexanoate, stannous succinate, stannous caprylate,and a combination thereof. Exemplary titanium catalysts include titaniumesters such as tetra-n-butyltitanate tetraisopropyltitanate,tetra-2-ethylhexyltitanate, tetraphenyltitanate, triethanolaminetitanate, organosiloxytitanium compounds, and dicarbonyl titaniumcompounds, such as titanium ethyl acetoacetate andbis(acetoacetonyl)-diisopropoxy titanium (IV). A titanium catalyst maybe used when the composition will be formulated as a room temperaturevulcanizing sealant composition. The amount of condensation reactioncatalyst depends on various factors including the amount of startingmaterial (i) and the types and amounts of any additional startingmaterials added to the composition, however the amount of condensationreaction catalyst may be 0.2 to 6, alternatively 0.5 to 3, parts byweight based on the weight of starting material (i).

The condensation reaction curable composition may further comprise oneor more additional ingredients distinct from ingredients (i) and (ii).Suitable additional ingredients are exemplified by (iii) a filler; (iv)a filler treating agent; (v) a crosslinker; (vi) a surface modifier,(vii) a drying agent; (viii) an extender, a plasticizer, or acombination thereof; (ix) a biocide; (x) a flame retardant; (xi) a chainlengthener; (xii) an endblocker; (xiii) a nonreactive binder; (xiv) ananti-aging additive; (xv) a water release agent; (xvi) a pigment; (xvii)a rheological additive; (xviii) a vehicle (such as a solvent and/or adiluent); (xix) a tackifying agent; (xx) a corrosion inhibitor; and acombination of two or more thereof. These additional ingredients andtheir amounts for use in a condensation reaction curable composition areexemplified by those disclosed, for example, in U.S. Pat. No. 9,156,948.

Starting material (iii) that may be added to the composition is afiller. The filler may comprise a reinforcing filler, an extendingfiller, or a combination thereof. For example, the composition mayoptionally further comprise ingredient (iii-1), a reinforcing filler,which when present may be added in an amount ranging from 0.1% to 95%,alternatively 1% to 60%, based on the weight of the composition. Theexact amount of starting material (iii-1) depends on various factorsincluding the form of the reaction product of the composition andwhether any other fillers are added. Examples of suitable reinforcingfillers include precipitated calcium carbonates and reinforcing silicafillers such as fume silica, silica aerogel, silica xerogel, andprecipitated silica. Suitable precipitated calcium carbonates includeWinnofil® SPM from Solvay and Ultrapflex® and Ultrapflex® 100 fromSpecialty Minerals, Inc. Fumed silicas are known in the art andcommercially available; e.g., fumed silica sold under the name CAB-O-SILby Cabot Corporation of Massachusetts, U.S.A.

The composition may optionally further comprise starting material(iii-2) an extending filler in an amount ranging from 0.1% to 95%,alternatively 1% to 60%, and alternatively 1% to 20%, based on theweight of the composition. Examples of extending fillers include crushedquartz, aluminum oxide, magnesium oxide, calcium carbonate such asground calcium carbonate, precipitated calcium carbonate, zinc oxide,talc, diatomaceous earth, iron oxide, clays, mica, chalk, titaniumdioxide, zirconia, sand, carbon black, graphite, or a combinationthereof. Extending fillers are known in the art and commerciallyavailable; such as a ground quartz sold under the name MIN—U-SIL by U.S.Silica of Berkeley Springs, W. Va. Examples of extending calciumcarbonates include CS-11 from Imerys, G3T from Huber, and Omyacarb 2Tfrom Omya.

The composition may optionally further comprise starting material (iv) atreating agent. The amount of starting material (iv) can vary dependingon factors such as the type of treating agent selected and the type andamount of particulates to be treated, and whether the particulates aretreated before being added to the composition, or whether theparticulates are treated in situ. However, starting material (iv) may beused in an amount ranging from 0.01% to 20%, alternatively 0.1% to 15%,and alternatively 0.5% to 5%, based on the weight of the composition.Particulates, such as the filler, the physical drying agent, certainflame retardants, certain pigments, and/or certain water release agents,when present, may optionally be surface treated with starting material(iv). Particulates may be treated with starting material (iv) beforebeing added to the composition, or in situ. Starting material (iv) maycomprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclicpolyorganosiloxane, a hydroxyl-functional oligosiloxane such as adimethyl siloxane or methyl phenyl siloxane, or a fatty acid. Examplesof fatty acids include stearates such as calcium stearate.

Some representative organosilicon filler treating agents that can beused as starting material (iv) include compositions normally used totreat silica fillers such as organochlorosilanes, organosiloxanes,organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanessuch as C₆H₁₃Si(OCH₃)₃, C₈H₁₇Si(OC₂H₅)₃, C₁₀H₂₁Si(OCH₃)₃,C₁₂H₂₅Si(OCH₃)₃, C₁₄H₂₉Si(OC₂H₅)₃, and C₆H₅CH₂CH₂Si(OCH₃)₃. Othertreating agents that can be used include alkylthiols, fatty acids,titanates, titanate coupling agents, zirconate coupling agents, andcombinations thereof.

Alternatively, starting material (iv) may comprise an alkoxysilanehaving the formula (XXIII): R¹³ _(p)Si(OR¹⁴)_((4−p)), where subscript pmay have a value ranging from 1 to 3, alternatively subscript p is 3.Each R¹³ is independently a monovalent organic group, such as amonovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to30 carbon atoms, alternatively 8 to 18 carbon atoms. R¹³ is exemplifiedby alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl,and octadecyl; and aromatic groups such as benzyl and phenylethyl. R¹³may be saturated or unsaturated, and branched or unbranched.Alternatively, R¹³ may be saturated and unbranched.

Each R¹⁴ is independently a saturated hydrocarbon group of 1 to 4 carbonatoms, alternatively 1 to 2 carbon atoms. Starting material (iv) isexemplified by hexyltrimethoxysilane, octyltriethoxysilane,decyltrimethoxysilane, dodecyltrimethoxysilane,tetradecyltrimethoxysilane, phenylethyltrimethoxysilane,octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinationsthereof.

Alkoxy-functional oligosiloxanes may also be used as treating agents.For example, suitable alkoxy-functional oligosiloxanes include those ofthe formula (XXIX): (R¹⁵O)_(q)Si(OSiR¹⁶ ₂R¹⁷)_((4−q)). In this formula,subscript q is 1, 2 or 3, alternatively subscript q is 3. Each R¹⁵ maybe an alkyl group. Each R¹⁶ may be an unsaturated monovalent hydrocarbongroup of 1 to 10 carbon atoms. Each R¹⁷ may be an unsaturated monovalenthydrocarbon group having at least 10 carbon atoms.

Alternatively, a polyorganosiloxane capable of hydrogen bonding isuseful as a treating agent. This strategy to treating surface of afiller takes advantage of multiple hydrogen bonds, either clustered ordispersed or both, as the means to tether the compatibilization moietyto the filler surface. The polyorganosiloxane capable of hydrogenbonding has an average, per molecule, of at least one silicon-bondedgroup capable of hydrogen bonding. The group may be selected from: anorganic group having multiple hydroxyl functionalities or an organicgroup having at least one amino functional group. The polyorganosiloxanecapable of hydrogen bonding means that hydrogen bonding is the primarymode of attachment for the polyorganosiloxane to a filler. Thepolyorganosiloxane may be incapable of forming covalent bonds with thefiller. The polyorganosiloxane may be free of condensable silyl groupse.g., silicon bonded alkoxy groups, silazanes, and silanols. Thepolyorganosiloxane capable of hydrogen bonding may be selected from thegroup consisting of a saccharide-siloxane polymer, an amino-functionalpolyorganosiloxane, and a combination thereof. Alternatively, thepolyorganosiloxane capable of hydrogen bonding may be asaccharide-siloxane polymer.

Starting material (v) is a crosslinker. Starting material (v) maycomprise a silane crosslinker having hydrolyzable groups or partial orfull hydrolysis products thereof. Starting material (v) has an average,per molecule, of greater than two substituents reactive with the alkoxygroups on starting material (i). Examples of suitable silanecrosslinkers for starting material (v) may have general formula (XXX):R¹⁰ _(k)Si(R⁹)_((4−k)), where each R¹⁰ is independently a monovalenthydrocarbon group such as an alkyl group; each R⁹ is a hydrolyzablesubstituent, for example, a halogen atom, an acetamido group, an acyloxygroup such as acetoxy, an alkoxy group, an amido group, an amino group,an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, ora methylacetamido group; and each instance of subscript k may be 0, 1,2, or 3. For starting material (v), subscript k has an average valuegreater than 2. Alternatively, subscript k may have a value ranging from3 to 4. Alternatively, each R⁹ may be independently selected fromhydroxyl, alkoxy, acetoxy, amide, or oxime. Alternatively, startingmaterial (v) may be selected from an acyloxysilane, an alkoxysilane, aketoximosilane, and an oximosilane.

Starting material (v) may comprise an alkoxysilane exemplified by adialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, suchas an alkyltrialkoxysilane; a tetraalkoxysilane; or partial or fullhydrolysis products thereof, or another combination thereof. Examples ofsuitable trialkoxysilanes include methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combinationthereof, and alternatively methyltrimethoxysilane. Examples of suitabletetraalkoxysilanes include tetraethoxysilane. The amount of thealkoxysilane that is used in the composition may range from 0.5 to 15,parts by weight per 100 parts by weight of starting material (i).

Starting material (v) may comprise an acyloxysilane, such as anacetoxysilane. Acetoxysilanes include a tetraacetoxysilane, anorganotriacetoxysilane, a diorganodiacetoxysilane, or a combinationthereof. The acetoxysilane may contain alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups suchas vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, orxylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinatedalkyl groups such as 3,3,3-trifluoropropyl. Exemplary acetoxysilanesinclude, but are not limited to, tetraacetoxysilane,methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane,propyltriacetoxysi lane, butyltriacetoxysi lane, phenyltriacetoxysilane,octyltriacetoxysilane, dimethyldiacetoxysilane,phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane, tetraacetoxysilane, and combinations thereof.Alternatively, starting material (v) may compriseorganotriacetoxysilanes, for example mixtures comprisingmethyltriacetoxysilane and ethyltriacetoxysilane. The amount of theacetoxysilane that is used in the curable silicone composition may rangefrom 0.5 to 15 parts by weight per 100 parts by weight of startingmaterial (i); alternatively 3 to 10 parts by weight of acetoxysilane per100 parts by weight of starting material (i).

Examples of silanes suitable for starting material (v) containing bothalkoxy and acetoxy groups that may be used in the composition includemethyldiacetoxymethoxysilane, methylacetoxydimethoxysilane,vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane,methyldiacetoxyethoxysilane, metylacetoxydiethoxysilane, andcombinations thereof.

Aminofunctional alkoxysilanes suitable for starting material (v) areexemplified by H₂N(CH₂)₂Si(OCH₃)₃, H₂N(CH₂)₂Si(OCH₂CH₃)₃,H₂N(CH₂)₃Si(OCH₃)₃, H₂N(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₃Si(OCH₃)₃,CH₃NH(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₅Si(OCH₃)₃, CH₃NH(CH₂)₅Si(OCH₂CH₃)₃,H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, H₂N(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,H₂N(CH₂)₂SiCH₃(OCH₃)₂, H₂N(CH₂)₂SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₅SiCH₃(OCH₃)₂,CH₃NH(CH₂)₅SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, and a combination thereof.

Suitable oximosilanes for starting material (v) includealkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane,propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanessuch as methoxytrioximosilane, ethoxytrioximosilane, andpropoxytrioximosilane; or alkenyltrioximosilanes such aspropenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanessuch as vinyloximosilane; alkenylalkyldioximosilanes such as vinylmethyl dioximosilane, vinyl ethyldioximosilane, vinylmethyldioximosilane, or vinylethyldioximosilane; or combinationsthereof.

Suitable ketoximosilanes for starting material (v) include methyltris(dimethylketoximo)silane, methyl tris(methylethylketoximo)silane,methyl tris(methylpropylketoximo)silane, methyltris(methylisobutylketoximo)silane, ethyl tris(dimethylketoximo)silane,ethyl tris(methylethylketoximo)silane, ethyltris(methylpropylketoximo)silane, ethyltris(methylisobutylketoximo)silane, vinyl tris(dimethylketoximo)silane,vinyl tris(methylethylketoximo)silane, vinyltris(methylpropylketoximo)silane, vinyltris(methylisobutylketoximo)silane, tetrakis(dimethylketoximo)silane,tetrakis(methylethylketoximo)silane,tetrakis(methylpropylketoximo)silane,tetrakis(methylisobutylketoximo)silane,methylbis(dimethylketoximo)silane, methylbis(cyclohexylketoximo)silane,triethoxy(ethylmethylketoxime)silane,diethoxydi(ethylmethylketoxime)silane,ethoxytri(ethylmethylketoxime)silane,methylvinylbis(methylisobutylketoximo)silane, or a combination thereof.

Alternatively, starting material (v) may be polymeric. For example,starting material (v) may comprise a disilane such asbis(triethoxysilyl)hexane), 1,4-bis[trimethoxysilyl(ethyl)]benzene, andbis[3-(triethoxysilyl)propyl] tetrasulfide.

Starting material (v) can be one single crosslinker or a combinationcomprising two or more crosslinkers that differ in at least one of thefollowing properties: hydrolyzable substituents and other organic groupsbonded to silicon, and when a polymeric crosslinker is used, siloxaneunits, structure, molecular weight, and sequence. Starting material (vi)is an adhesion promoter. Suitable adhesion promoters for startingmaterial (vi) may comprise a hydrocarbonoxysilane such as analkoxysilane, a combination of an alkoxysilane and a hydroxy-functionalpolyorganosiloxane, an aminofunctional silane, a mercaptofunctionalsilane, or a combination thereof. Adhesion promoters are known in theart and may comprise silanes having the formula R²⁴ _(t)R²⁵_(u)Si(OR²⁶)_(4−(t+u)) where each R²⁴ is independently a monovalentorganic group having at least 3 carbon atoms; R²⁵ contains at least oneSiC bonded substituent having an adhesion-promoting group, such asamino, epoxy, mercapto or acrylate groups; subscript t has a valueranging from 0 to 2; subscript u is either 1 or 2; and the sum of (t+u)is not greater than 3. Alternatively, the adhesion promoter may comprisea partial condensate of the above silane. Alternatively, the adhesionpromoter may comprise a combination of an alkoxysilane and ahydroxy-functional polyorganosiloxane.

Alternatively, the adhesion promoter may comprise an unsaturated orepoxy-functional compound. The adhesion promoter may comprise anunsaturated or epoxy-functional alkoxysilane. For example, thefunctional alkoxysilane can have the formula (XX): R²⁷_(v)Si(OR²⁸)_((4−v)), where subscript v is 1, 2, or 3, alternativelysubscript v is 1. Each R²⁷ is independently a monovalent organic groupwith the proviso that at least one R²⁷ is an unsaturated organic groupor an epoxy-functional organic group. Epoxy-functional organic groupsfor R²⁷ are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.Unsaturated organic groups for R²⁷ are exemplified by3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalenthydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl. Each R²⁸is independently a saturated hydrocarbon group of 1 to 4 carbon atoms,alternatively 1 to 2 carbon atoms. R²⁸ is exemplified by methyl, ethyl,propyl, and butyl.

Examples of suitable epoxy-functional alkoxysilanes include3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,(epoxycyclohexyl)ethyldimethoxysilane,(epoxycyclohexyl)ethyldiethoxysilane and combinations thereof. Examplesof suitable unsaturated alkoxysilanes include vinyltrimethoxysilane,allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane,undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane,3-methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyl triethoxysilane, and combinationsthereof.

Alternatively, the adhesion promoter may comprise an epoxy-functionalsiloxane such as a reaction product of a hydroxy-terminatedpolyorganosiloxane with an epoxy-functional alkoxysilane, as describedabove, or a physical blend of the hydroxy-terminated polyorganosiloxanewith the epoxy-functional alkoxysilane. The adhesion promoter maycomprise a combination of an epoxy-functional alkoxysilane and anepoxy-functional siloxane. For example, the adhesion promoter isexemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and areaction product of hydroxy-terminated methylvinylsiloxane with3-glycidoxypropyltrimethoxysilane, or a mixture of3-glycidoxypropyltrimethoxysilane and a hydroxy-terminatedmethylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilaneand a hydroxy-terminated methylvinyl/dimethylsiloxane copolymer.

Alternatively, the adhesion promoter may comprise an aminofunctionalsilane, such as an aminofunctional alkoxysilane exemplified byH₂N(CH₂)₂Si(OCH₃)₃, H₂N(CH₂)₂Si(OCH₂CH₃)₃, H₂N(CH₂)₃Si(OCH₃)₃,H₂N(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₃Si(OCH₃)₃, CH₃NH(CH₂)₃Si(OCH₂CH₃)₃,CH₃NH(CH₂)₅Si(OCH₃)₃, CH₃NH(CH₂)₅Si(OCH₂CH₃)₃,H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, H₂N(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,H₂N(CH₂)₂SiCH₃(OCH₃)₂, H₂N(CH₂)₂SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₅SiCH₃(OCH₃)₂,CH₃NH(CH₂)₅SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂,N-(3-(trimethoxysilyl)propyl)ethylenediamine, and a combination thereof.

Alternatively, the adhesion promoter may comprise a mercaptofunctionalalkoxysilane, such as 3-mercaptopropyltrimethoxysilane or3-mercaptopropyltriethoxysilane.

The exact amount of starting material (vi) depends on various factorsincluding the type of adhesion promoter selected and the end use of thecomposition and its reaction product. However, starting material (vi),when present, may be added to the composition in an amount ranging from0.01 to 50 weight parts based on the weight of the composition,alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5weight parts. Starting material (vi) may be one adhesion promoter.Alternatively, starting material (vi) may comprise two or more differentadhesion promoters that differ in at least one of the followingproperties: structure, viscosity, average molecular weight, polymerunits, and sequence.

When selecting ingredients for the condensation reaction curablecomposition described above, there may be overlap between types ofstarting materials because certain starting materials described hereinmay have more than one function. For example, certain alkoxysilanes maybe useful as filler treating agents, as adhesion promoters, and ascrosslinkers.

Alternatively, the crosslinker, the filler, and the adhesion promotermay each be present in the composition. In this embodiment, thecrosslinker may comprise an alkyl trialkoxysilane, such asmethyltrimethoxysilane; the filler may comprise an extending filler suchas calcium carbonate; and the adhesion promoter may comprise analkoxysilane other than the crosslinker, such asN-(3-(trimethoxysilyl)propyl)ethylenediamine,3-mercaptopropyltrimethoxysilane, or both

The composition described above may be prepared as a one partcomposition, for example, by combining all ingredients by any convenientmeans, such as mixing. For example, a one-part composition may be madeby optionally combining (e.g., premixing) (i) the alkoxy-functionalpolyorganosiloxane with all or part of (iii) the filler, when present;and mixing this with a pre-mix comprising the catalyst (ii) and, whenpresent (v) the crosslinker. Other additives such as an anti-agingadditive and a pigment may be added to the mixture at any desired stage.A final mixing step may be performed under substantially anhydrousconditions, and the resulting compositions are generally stored undersubstantially anhydrous conditions, for example in sealed containers,until ready for use.

Alternatively, the composition may be prepared as a multiple part (e.g.,2 part) composition when a crosslinker is present. In this instance thecatalyst and crosslinker are stored in separate parts, and the parts arecombined shortly before use of the composition. For example, a two partcurable composition may be prepared by combining ingredients comprisingthe alkoxy-functional polyorganosiloxane and the crosslinker to form afirst (curing agent) part by any convenient means such as mixing. Asecond (base) part may be prepared by combining starting materialscomprising a catalyst and the alkoxy-functional polyorganosiloxane byany convenient means such as mixing. The starting materials may becombined at ambient or elevated temperature and under ambient oranhydrous conditions, depending on various factors including whether aone part or multiple part composition is selected. The base part andcuring agent part may be combined by any convenient means, such asmixing, shortly before use. The base part and curing agent part may becombined in relative amounts of base: curing agent ranging from 1:1 to10:1.

The equipment used for mixing the starting materials is not specificallyrestricted. Examples of suitable mixing equipment may be selecteddepending on the type and amount of each ingredient selected. Forexample, agitated batch kettles may be used for relatively low viscositycompositions, such as compositions that would react to form gums orgels. Alternatively, continuous compounding equipment, e.g., extruderssuch as twin screw extruders, may be used for more viscous compositionsand compositions containing relatively high amounts of particulates.Exemplary methods that can be used to prepare the compositions describedherein include those disclosed in, for example, U.S. Patent PublicationsUS 2009/0291238 and US 2008/0300358.

These compositions made as described above may be stable when the storedin containers that protect the compositions from exposure to moisture,but these compositions may react via condensation reaction when exposedto atmospheric moisture.

EXAMPLES

These examples are intended to illustrate some embodiments of theinvention and should not be interpreted as limiting the scope of theinvention set forth in the claims. In the examples below, the exampleswere performed under conditions including an oxidant, e.g., 2% oxygen.The following starting materials and abbreviations are defined asfollows:

Abbreviation Definition TMDS 1,1,3,3-tetramethyldisiloxane, example ofstarting material A) M′D′M′ 1,1,3,5,5-pentamethyltrisiloxane, example ofstarting material A) M′T^(Pr) Siloxane oligomer having 3 (Me₂HSiO_(1/2))units and having one (PrSiO_(3/2)) unit, where Me represents a methylgroup and Pr represents a propyl group. VTMS Vinyltrimethoxysilane,example of starting material B) [Ir(COD)Cl]2 [Ir(1,5-cyclooctadiene)Cl]₂example of starting material C) THF Tetrahydrofuran, example of asolvent GC-FID Gas chromatography with flame ionization detection GC-MSGas chromatography, mass spectrometry MeSi(OMe)₃ Methyl trimethoxysilaneTi(OiPr)₂(EAA)₂ Titanium Diisopropoxide Di(Ethyl Acetoacetate) Ti(OBu)₄Titanium tetrabutoxide (MeO)₃Si(CH₂)SH Thiopropyl Trimethoxysilane(MeO)₃Si(CH₂)₃NH(CH₂)₂NH₂ Aminoethylaminopropyl Trimethoxysilane MeMethyl Et Ethyl Vi Vinyl

“Yield” means molar amount alkoxy-functional organohydrogensiloxaneoligomer produced/molar amount alkoxy-functional organohydrogensiloxaneoligomer possible based on the amount of limiting reagent (thealiphatically unsaturated alkoxysilane). “Selectivity” means the ratioof linear isomer/branched isomer of the alkoxy-functionalorganohydrogensiloxane (where isomers have the same molecular weight).

Example 1

In an air-free glovebox, a mixture of 13.8 g of VTMS and 15.2 g of TMDSwas loaded into a 100 mL round bottom flask. The mixture was thenpre-heated to 70° C., vigorously stirred with a stirbar, and then 226 μLof a 0.005 M solution of [Ir(1,5-cyclooctadiene)Cl]₂ in toluene wasadded. An exotherm and bubbling were initially observed. The reactionmixture was allowed to react for 16 h. The reaction mixture was thenpurified by distillation, which resulted in a light fraction (solvents,unreacted reagents, and light byproducts), a desired product fraction,and a heavy fraction which was left behind in the distillation flask.The yield of the desired product fractions was 14.73 g (50.8%), andconsisted of approximately 93% of the linear isomer, 2% of the branchedisomer, and 5% of the dehydrogenative silylation product. Significantamounts of unreacted starting materials were observed, and interestinglyonly trace amounts of the double hydrosilylation product were observed.

Example 2 (Comparative)

In an air-free glovebox, a mixture of 1.1 g of VTMS, 1 g of TMDS, and0.25 g of dodecane (internal standard) was added to a 20 mLscintillation vial containing a stirbar. Then 30 μL of a 0.01 M solutionof Rh(PPh₃)₃Cl in THF was added (this reagent solution was heated to 60°C. with stirring in order to dissolve the poorly soluble catalyst).After stirring at room temperature for 30 min, the reaction mixture washeated to 50° C. for 16 h. At this stage, an aliquot (˜150 μL) of thereaction mixture was withdrawn and injected into a GC vial, and dilutedwith ˜1 mL of xylene. The reaction was analyzed by GC-FID and GC-MS.Analysis indicated ˜54% yield of the linear product with 8% of thebranched isomer detected. A small amount of unreacted starting materialswere observed. This Example 2 shows less selectivity than example 1 tothe desired beta-adduct in the product.

Example 3 (Comparative)—Preparation of Ethyltrimethoxysilyl-TerminatedTetramethyldisiloxane

In an air-free glovebox, a mixture of 1.1 g of VTMS, 1 g of TMDS, and0.25 g of dodecane (internal standard) was added to a 20 mLscintillation vial containing a stirbar. Then 30 μL of a 0.01 M solutionof Pt in THF in the form of Karstedt's catalyst (supplied as 2% inxylene, Sigma Aldrich) was added (this reagent solution was heated to60° C. with stirring in order to dissolve the poorly soluble catalyst).After stirring at room temperature for 30 min, the reaction mixture washeated to 50° C. for 16 h. At this stage, an aliquot (˜150 μL) of thereaction mixture was withdrawn and injected into a GC vial, and dilutedwith ˜1 mL of xylene. The reaction was analyzed by GC-FID and GC-MS.Analysis indicated ˜46% yield of the linear product with 26% of thebranched isomer detected. A small amount of unreactedtetramethyldisiloxane was observed but all of the vinyltrimethoxysilanewas observed.

Example 4 (Comparative)—Preparation ofdi(trimethoxysilylethyl)pentamethyltrisiloxane (M′D′M′ EHM)

A solution of 1% Pt catalyst in toluene was prepared. VTM in an amountof 18.05 g was added at a rate of 275 μL/min to a flask containing 11.97g M′D′M′ in at a temperature of 40° C. under N₂ with rapid stirringwhile cooling the flask, by means of a syringe pump. 5% of the total VTMwas initially added, followed by 10 pm Pt catalyst (39 μL of the 1%solution Pt in toluene) to start the exotherm, and then the addition ofthe remaining VTM was begun. The temperature was monitored by athermocouple and kept below 80° C. by controlling the addition rate.After the complete addition of VTM, the reaction solution was stirred at75° C. for 0.5 h, allowed to cool, and characterized by GC which showedthe product mixture contained 10% monofunctional oligomer, 68%difunctional oligomer, and 20% trifunctional oligomer. The sample waspurified by distillation under 1 Torr (0.1333 kPa) to give 16.9 g M′D′M′EHM (yield: 56%) with a boiling point of 135-137° C. at 1 Torr (0.1333kPa). The sample was characterized by GC, 1H, and ²⁹Si NMR. The finalproduct was composed of 66% β isomers of M′D′H′ EHM and 34% a isomers ofM′D′M′ EHM; 60% D-H isomer (first product structure in the reactionscheme shown below) and 40% M-H isomer (second product structure in thereaction scheme shown below). 1H NMR (CDCl₃): δ 4.69 (M-H), 4.62 (D-H),3.55 (—OCH₃), 1.06 (—CH₃ from α isomer), 0.56 (—CH₂CH₂— from β isomer),0.25 to 0 (—CH₃ and —CH(Me)—). ²⁹Si NMR (CDCl₃): δ11 to 9 (M-D′), 9 to 7(M-D), −6 to −8 (M′), −19 to −23 (D), −35 to −38 (D′), −40 to −43 (7).

Example 5 (Prophetic)—Preparation ofdi(trimethoxysilylethyl)pentamethyltrisiloxane (M′D′M′ EHM)

A 0.005 M solution of [Ir(1,5-cyclooctadiene)Cl]₂ in toluene will beprepared. A three-neck round bottom flask fitted with a thermocouple anda cold water condenser will be charged with 9.96 g of this catalyst and15.04 g VTM. The flask will be purged with N₂, and the mixture in theflask will be heated to 80° C., followed by the addition of catalystsolution (1 mL). After 17 h stirring at 80° C. under N₂, the reactionmixture will be allowed to cool to room temperature of 25° C. and willbe analyzed by GC.

Example 6 (Comparative)—Preparation of di(trimethoxysilylethyl) SiloxaneOligomer (Pr-T EHM)

The procedure of Example 4 was repeated, except that M′T^(Pr) (15.0 g),VTM (15.0 g), and platinum catalyst solution in toluene 39 μL) were usedas starting materials. The crude product contained 14% monofunctionaloligomer, 54% difunctional oligomer, and 31% trifunctional oligomer byGC (FID). The sample was purified by distillation under 1 Torr (0.1333kPa) to give 13.5 g pure Pr-T EHM (yield: 45%). This was characterizedby GC (retention time: 30.8-31.1 min), ¹H, and ²⁹Si NMR. This sample wascomposed of 70% βisomer of Pr-T EHM and 30% a isomer of Pr-T EHM. ¹H NMR(CDCl₃): δ 4.69 (Si—H), 3.55 (—OCH₃), 1.36 (CH₃CH₂CH₂—), 1.09 (—CH₃ fromα isomer), 0.92 (CH₃CH₂CH₂—), 0.56 (—CH₂CH₂— from βisomer), 0.45(CH₃CH₂CH₂—), 0.2 to 0 (—SiCH₃). ²⁹Si NMR (CDCl₃): δ10 to 7 (M), −6 to−8 (M′), −40 to −43 (T-OMe), −63 to −65 (T-Pr).

Example 7—Preparation of di(trimethoxysilylethyl-pentamethyltrisiloxane(Pr-T EHM) (Prophetic)

The procedure of Example 5 will be repeated, except that M′T^(Pr) (29.7g), VTM (29.7 g), and a 0.005 M solution of [Ir(1,5-cyclooctadiene)Cl]₂in toluene was added will be used as starting materials. The reactionwill be conducted at 80° C. for 7 h.

Example Product β/α ratio 4 (comparative) M′D′M′ EHM 66/34 6(comparative) Pr-T EHM 70/30

Example 8—Preparation of Ethyl(dimethoxymethyl)silyl-terminatedTetramethyldisiloxane

To a 250 mL round bottom flask containing 13.84 g HSiMe₂OSiMe₂H and astirbar, was affixed an addition funnel containing 9.080 g ofViSiMe(OMe)₂ (where Me represents methyl, and Vi represents vinyl). 0.1mL of [Ir(COD)Cl]₂ solution in toluene (0.05 M in Ir) was added to thevinyl reagent. The ViSiMe(OMe)₂ was dripped into the flask at 1drop/sec, and there was a gradual exotherm up to ˜55C. At this point,˜0.1 mL of [Ir(COD)Cl]₂ solution was added to the flask, and thetemperature began to rise at a somewhat faster rate. The drip of theViSiMe(OMe)₂ was continued at 1 drop/sec until complete, and thetemperature maxed out at 70° C. After cooling to 50° C., an additional0.1 mL of [Ir(COD)Cl]₂ solution was added; no additional exotherm wasobserved, and so the reaction was judged as complete. A gaschromatography-mass spectrometry/flame ionization detection (GC-MS/FID)of the reaction mixture indicated high conversion to the productHSiMe₂OSiMe₂CH₂CH₂SiMe(OMe)₂ (˜91.2%). This example demonstrated thatthe catalyst is active towards substrates in which there is variation inthe formula ViSiMe_(x)(OMe)_((3−x)), where subscript x can be 0 to 3.

Example 9—Preparation of Ethyl(triethoxy)silyl-terminatedTetramethyldisiloxane

A 250 mL flask was loaded with 71.57 g of tetramethyldisiloxane, and tothe flask was affixed a reflux condenser, addition funnel, and septathrough which was inserted thermocouples for temperature logging andcontrol. The addition funnel was loaded with 78 g ofvinyltriethoxysilane (VTM) as well as 0.4 mL of 0.05 M Ir ([Ir(COD)Cl]₂in toluene). The contents of the flask were heated to 50° C. and then adrip of the VTM/Ir mixture was fed into the flask at 1 drop/sec. Anexotherm initiated and was allowed to gradually proceed up to 80° C. bythe end of the addition. After the addition was completed, the reactionmixture was externally heated at 70° C. for an additional 2 h. At thispoint, the reaction mixture was analyzed by GC-FID. The mass balancebased on species derived from ViSi(OEt)₃ was 0.6% ViSi(OEt)₃, 3.2%EtSi(OEt)₃, and 95.3% HSiMe₂OSiMe₂CH₂CH₂Si(OEt)₃, 1.6%HSiMe₂OSiMe₂CMeHSi(OEt)₃, and 0.6% HSiMe₂OSiMe₂CHCHSi(OEt)₃. Thisexample demonstrates that variation in the identity of the alkoxy groupsin (B) the aliphatically unsaturated alkoxysilane can be tolerated bythe catalyst.

Example 10—Preparation of Propyl(trimethoxy)silyl-terminatedTetramethyldisiloxane

A 250 mL flask was loaded with 25 g of TMDS, and affixed with acondenser, thermocouples for temperature control and logging, and anaddition funnel pre-loaded with AllylSi(OMe)₃. After preheating to 50°C., the addition of AllylSi(OMe)₃ was started at 2 drop/sec. An initialsmall exotherm was observed, heating to 55° C., but after that thetemperature began to fall. At this point (25% of AllylSi(OMe)₃ added)0.4 mL of additional Ir solution was added, and no additional exothermwas observed. The flask was then heated to 70° C. for 1 h. At thispoint, a GC aliquot indicated a yield of 7.5% ofHSiMe₂OSiMe₂(CH₂)₃Si(OMe)₃. Other detected byproducts were 0.7%HSiMe₂OSiMe₂(C₃H₄)Si(OMe)₃, 6.5% Me₃Si(CH₂)₃Si(OMe)₃, 58.8% unreactedCH-₂CH₂CH₂Si(OMe)₃, 16.9% isomerized CH₃CHCHSi(OMe)₃, 9.3%CH₃CH₃CH₃Si(OMe)₃. Other trace byproducts were detected but furtheridentification was difficult. This example demonstrates that thecatalyst is tolerant of substrates in which methylene spacers are placedbetween the terminal aliphatic unsaturation in (B) the alkoxysilane,e.g., Vi(CH₂)_(x)Si(OMe)₃, under the conditions tested in this example.

Example 11—Preparation of Ethyl(trimethoxy)silyl-terminatedPentamethyldisiloxane

To a flask containing 19.07 g HSiMe₂OSiMe₃ and a stirbar, was affixed anaddition funnel containing 12.7 g ViSi(OMe)₃, a condenser, and a septathrough which was inserted thermocouples for temperature control. 0.1 mLof [Ir(COD)Cl]₂ solution in toluene (0.05 M in Ir) was added to thevinyl reagent. After preheating the flask to 50° C., the ViSi(OMe)₃/Irmixture was added dropwise at 1 drop/sec. A 2° C. exotherm was initiallynoted, but rapidly diminished and no further exotherm was observed.After the addition of vinyl reagent and Ir was complete, the reactionmixture was allowed to react for 15 min and an aliquot for GC-MS wasrecorded. Very little reaction had occurred, with 0.7%Me₃SiOSiMe₂(CH₂)₂Si(OMe)₃ and 6.1% HSiMe₂OSiMe₂(CH₂)₂Si(OMe)₃. Thelatter apparently arises from the redistribution of the startingmaterial; Me₃SiOSiMe₃ is also observed. This example demonstrated thatcatalytic hydrosilylation of hydrosilane substrates containing less thantwo Si—H groups can be performed under the conditions tested in thisexample.

Example 12—Preparation of Ethyl(trimethoxy)silyl-terminatedPolydimethylsiloxane

To a vial containing of 5.00 g of a polymer primarily composed ofHSiMe₂O(SiMe₂O)₂₀SiMe₂H was added 1.01 g of ViSi(OMe)₃. The mixture wasstirred until blended, and then 153 μL of [Ir(COD)Cl]₂ was added (0.05Min Ir). A small exotherm was felt in the vial, though it is difficult totell by hand. After stirring at room temperature for 72 h, the reactionmixture was dissolved in d8-toluene and analyzed by 1H NMR. Mass balanceof the ViSi(OMe)₃ reagent indicated that 46.5% remained unreacted, 20.9%had undergone linear hydrosilylation onto the polymer, and 32.6% hadbeen hydrogenated into EtSi(OMe)₃. All of the initial Si—H had beenconsumed. This example demonstrates that the Ir catalyst is able tocatalyze hydrosilylation on polymeric substrates, although there aresome byproducts.

Composition Example (Reference 1)—Compounding Procedure for SealantComposition Samples

To a speed mixer cup was added 210.88 g of a trimethoxy-functionalpolydimethylsiloxane prepared by hydrosilylation reaction of anethyltrimethoxysilyl-terminated tetramethyldisiloxane (prepared in anexample as described above) and an α,ω-vinyl-terminatedpolydimethylsiloxane. A slurry of methyltrimethoxysilane, tetra-n-butoxytitanate, 3-mercaptopropyltrimethoxysilane, slurry of 80% titanium ethylacetoacetate 20% methyltrimethoxysilane, andN-(3-(trimethoxysilyl)propyl)ethylenediamine was prepared in a ratioequivalent to the ratio shown in a table below. From this slurry, 13.16g was added to the speed mixer cup. The cup was mixed in a DAC 600.2VAC-P Speedmixer for 30 seconds at 800 revolutions per minute (rpm),then 30 seconds at 1500 rpm. Next, 149.2 g of precipitated calciumcarbonate was added to the cup and mixed 30 seconds at 800 rpm, and 30seconds at 1500 rpm. The sides and bottom of the cup were then scrapedby hand with a spatula. Next 26.76 g of ground calcium carbonate wasadded to the cup and it was mixed for 30 seconds at 800 rpm and 30seconds at 1500 rpm. Again, the sides and bottom of the cup were handscraped with a spatula. Finally, the cup was fitted with a cap thatcontained a hole as to allow the contents of the cup to be exposed to avacuum environment. The cup was de-aired by mixing 30 seconds at 800 rpmand 5 psi (34.5 kPa), 30 seconds at 1500 rpm and 5 psi (34.5 kPa), and30 seconds at 800 rpm and 14.7 psi (101.35 kPa) The resulting sealantcomposition was transferred to Semco® tubes via a hand operated cuppress.

In these comparative examples 13 and 14, two comparative samples wereprepared using the procedure above and including the starting materialsin the table below.

Amount Speedmixer Starting Materials (g) Comparative sample usingPolydimethylsiloxane 100% end capped with 70% β 210.88polydimethylsiloxane 100% ethyltrimethoxysilyl group containingendcapped with the tetramethyldisiloxane and 30% α ethyltrimethoxyethyltrimethoxysilyl-terminated silyl group containingtetramethyldisiloxane (the tetramethyldisiloxane prepared inethyltrimethoxysilyl-terminated tetramethyldisiloxane ComparativeExample 3) prepared in comparative Example 3) Precipitated CalciumCarbonate 149.2 Ground Calcium Carbonate 26.76 Methyltrimethoxysilane7.36 Tetra-n-butoxy titanate 1.32 3-Mercaptopropyltrimethoxysilane 0.76Slurry 80% Titanium Ethyl Acetoacetate 20% 3.52 MethyltrimethoxysilaneN-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.2

In these examples 15 and 16, two sealant composition samples will beprepared according to the table below.

Amount Speedmixer Component (g) (Prophetic) Samples will be preparedPolydimethylsiloxane 100% end capped 210.88 using a polydimethylsiloxanecapped with the ethyltrimethoxy-functional with a product prepared asdescribed siloxanes prepared in Example 1, 2, 6, or 8 in Example 1, 2,6, and 8 Precipitated Calcium Carbonate 149.2 Ground Calcium Carbonate26.76 Methyltrimethoxysilane 7.36 Tetra-n-butoxy titanate 1.323-Mercaptopropyltrimethoxysilane 0.76 Slurry 80% Titanium EthylAcetoacetate 3.52 20% MethyltrimethoxysilaneN-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.2

The composition samples prepared as described above will be evaluatedusing the following test methods for Tack Free Time (TFT) and Skin OverTime (SOT).

TFT was tested as follows. A 100 mil slab of sealant was drawn down on apiece of polyethylene terephthalate (PET). A small strip of PET is thenlightly pressed onto the surface of the sealant to check for cure. Whenno sealant is transferred to the strip of PET, the sealant is consideredtack free.

SOT was tested as follows. A 100 mil slab of sealant was drawn down on apiece of PET. A sealant is considered to have become skinned over whenno sealant transfers to a gloved or bare finger when lightly touched.

The table below shows testing done on the comparative sealantcomposition samples prepared as described above. On an 8 millimeter (mm)parallel plate constant stress rheometer, a dollop of uncured sealantwas pressed to 1.829 mm and trimmed with a razor blade. The sealant wascured in place for the time specified. Next, a constant stress of 0.5psi (3.45 kPa) was applied for the time specified. The stress was thenreleased and the sealant was allowed to recover for five minutes.Sealant with a faster cure will creep less during the stress period, andwill recover more closely to zero during the recovery period.

TFT SOT Sample # Description (min) (min) Sealant Comparative sampleusing polydimethylsiloxane 40 19 Composition 1 100% endcapped with theethyltrimethoxysilyl- (comparative) terminated tetramethyldisiloxaneprepared in Comparative Example 3) 70% β 30% α Sealant Comparativesample using polydimethylsiloxane 36 22 Composition 2 100% endcappedwith the ethyltrimethoxysilyl- (comparative) terminatedtetramethyldisiloxane prepared in Comparative Example 3)

Composition Example (Reference 2)—Compounding Procedure for SealantComposition Samples (Reference 2)

To a speed mixer cup was added the polymer referenced in a table below.A slurry of methyltrimethoxysilane, slurry of 80% titanium ethylacetoacetate 20% methyltrimethoxysilane, tetra-n-butoxy titanate,3-mercaptopropyltrimethoxysilane, andN-(3-(trimethoxysilyl)propyl)ethylenediamine was prepared in a ratioequivalent to the ratio seen in the above formulations. Note that notall starting materials were in every slurry, see tables below. To thecup was added this slurry equivalent to the sum of its startingmaterials. The cup was then mixed in a DAC 600.2 VAC-P Speedmixer forone minute at 1500 rpm. Next, the allotment of precipitated calciumcarbonate and ground calcium carbonate, where used, was added to the cupand mixed 30 seconds at 2000 rpm. Finally, the cup was fitted with a capthat contained a hole as to allow the contents of the cup to be exposedto a vacuum environment. The cup was de-aired by mixing 30 seconds at800 rpm and 5 psi (34.5 kPa), 30 seconds at 1500 rpm and 5 psi (34.5kPa), and 30 seconds at 800 rpm and 14.7 psi (101.35 kPa). The resultingsealant was transferred to Semco® tubes via a hand operated cup press. Areasonable variance was allowed when adding ingredients.

Test Method Reference Example 3—Creep and Recovery Procedure

On an AR 550 constant stress parallel plate rheometer, a disc of sealantprepared according to Reference Example 3, 8 mm in diameter, and 1.829mm in thickness was cured for forty-five minutes. Next, a constantstress of 0.5 psi (3.45 kPa) was applied to the sealant for twentyseconds, and the strain was recorded as creep. The stress was released,and the recovery was measured for two minutes. Sealants that cure fasterwill have lower creep values, and will have recovery values closer tozero.

Test Method Reference Example 4—Tack-Free Time Procedure

A 100-mil thick slab of sealant prepared according to Reference Example3 was drawn down on PET and cured in standard laboratory conditions (RTand ambient pressure). A small piece of PET was lightly pressed onto thesurface of the sealant and peeled off. Tack-free time was recorded whenthe small piece of PET was peeled from the sealant with no residue.

Test Method Reference Example 5—Skin-Over Time Procedure

A 100-mil thick slab of sealant prepared according to Reference Example3 was drawn down on PET and cured in standard laboratory conditions.Skin-over time was recorded when no sealant transferred to a finger tipwhen lightly touched.

Amount Speedmixer Component (g) Sample 17 Polydimethylsiloxane 100% endcapped 207.19 with 66.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 33.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Comparative Example 3) PrecipitatedCalcium Carbonate 150.04 Methyltrimethoxysilane 8.88 Slurry 80% TitaniumEthyl Acetoacetate 3.70 20% Methyltrimethoxysilane N-(3- 0.19(Trimethoxysilyl)propyl)ethylenediamine

Amount Speedmixer Component (g) Sample 18 Polydimethylsiloxane 100% endcapped 207.19 with 76.6% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 23.4% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane used in this sample was a blend prepared from theethyltrimethoxysilyl group containing tetramethyldisiloxanes inComparative Example 3 and Example 1 to achieve the 76.6/23.4 isomerratio) Precipitated Calcium Carbonate 150.04 Methyltrimethoxysilane 8.88Slurry 80% Titanium Ethyl Acetoacetate 3.70 20% MethyltrimethoxysilaneN-(3- 0.19 (Trimethoxysilyl)propyl)ethylenediamine

Amount Speedmixer Component (g) Sample 19 Polydimethylsiloxane 100% endcapped 207.19 with 86.8% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 13.2% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane was a blend prepared from the ethyltrimethoxysilylgroup containing tetramethyldisiloxanes in Comparative Example 3 andExample 1 to achieve 86.8/13.2 isomer ratio) Precipitated CalciumCarbonate 150.04 Methyltrimethoxysilane 8.88 Slurry 80% Titanium EthylAcetoacetate 3.70 20% Methyltrimethoxysilane N-(3- 0.19(Trimethoxysilyl)propyl)ethylenediamine

Amount Speedmixer Component (g) Sample 20 Polydimethylsiloxane 100% endcapped 207.19 with 96.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 3.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Example 1) Precipitated CalciumCarbonate 150.04 Methyltrimethoxysilane 8.88 Slurry 80% Titanium EthylAcetoacetate 3.70 20% Methyltrimethoxysilane N-(3- 0.19(Trimethoxysilyl)propyl)ethylenediamine

Amount Speedmixer Component (g) Sample 21 Polydimethylsiloxane 100% endcapped 207.19 with 65% β 35% α di-ethyltrimethoxysilyl groups (preparedas in Comparative Example 6) Precipitated Calcium Carbonate 150.04Methyltrimethoxysilane 8.88 Slurry 80% Titanium Ethyl Acetoacetate 3.7020% Methyltrimethoxysilane N-(3- 0.19(Trimethoxysilyl)propyl)ethylenediamine

Amount Speedmixer Component (g) Sample 22 Polydimethylsiloxane 100% endcapped 207.19 (prophetic) with 95% β 5% α di-ethyltrimethoxysilyl groupsPrecipitated Calcium Carbonate 150.04 Methyltrimethoxysilane 8.88 Slurry80% Titanium Ethyl Acetoacetate 3.70 20% Methyltrimethoxysilane N-(3-0.19 (Trimethoxysilyl)propyl)ethylenediamine

Creep Recovery SOT TFT Sample Description (%) (%) (min) (min) Sample 1766.4% β ETM 124.6 14 20 46 (comparative) Sample 18 76.6% β ETM 78.8 6.218 36 (comparative) Sample 19 86.8% β ETM 43.6 2.8 13 32 (comparative)Sample 20 96.4% β ETM 22.7 1.5 13 25 (practical) Sample 21   65% β EHM26.0 1.4 10 23 (comparative) Sample 22   95% β EHM 22.9 1.2 7 17(practical)

Amount Speedmixer Component (g) Sample 23 Polydimethylsiloxane 100% endcapped 163.47 with 66.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 33.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Comparative Example 3) PrecipitatedCalcium Carbonate 118.53 Ground Calcium Carbonate 9.75Methyltrimethoxysilane 4.83 Slurry 80% Titanium Ethyl Acetoacetate 2.2520% Methyltrimethoxysilane Tetra-n-butoxy titanate 0.843-Mercaptopropyltrimethoxysilane 0.33

Amount Speedmixer Component (g) Sample 24 Polydimethylsiloxane 100% endcapped 163.47 with 76.6% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 23.4% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane used in this sample was a blend prepared from theethyltrimethoxysilyl group containing tetramethyldisiloxanes inComparative Example 3 and Example 1 to achieve the 76.6/23.4 isomerratio) Precipitated Calcium Carbonate 118.53 Ground Calcium Carbonate9.75 Methyltrimethoxysilane 4.83 Slurry 80% Titanium Ethyl Acetoacetate2.25 20% Methyltrimethoxysilane Tetra-n-butoxy titanate 0.843-Mercaptopropyltrimethoxysilane 0.33

Amount Speedmixer Component (g) Sample 25 Polydimethylsiloxane 100% endcapped 163.47 with 86.8% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 13.2% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane was a blend prepared from the ethyltrimethoxysilylgroup containing tetramethyldisiloxanes in Comparative Example 3 andExample 1 to achieve 86.8/13.2 isomer ratio) Precipitated CalciumCarbonate 118.53 Ground Calcium Carbonate 9.75 Methyltrimethoxysilane4.83 Slurry 80% Titanium Ethyl Acetoacetate 2.25 20%Methyltrimethoxysilane Tetra-n-butoxy titanate 0.843-Mercaptopropyltrimethoxysilane 0.33

Amount Speedmixer Component (g) Sample 26 Polydimethylsiloxane 100% endcapped 163.47 with 96.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 3.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Example 1) Precipitated CalciumCarbonate 118.53 Ground Calcium Carbonate 9.75 Methyltrimethoxysilane4.83 Slurry 80% Titanium Ethyl Acetoacetate 2.25 20%Methyltrimethoxysilane Tetra-n-butoxy titanate 0.843-Mercaptopropyltrimethoxysilane 0.33

Amount Speedmixer Component (g) Sample 27 Polydimethylsiloxane 100% endcapped with 65% β 163.47 35% α di-ethyltrimethoxysilyl groups (preparedas in Comparative Example 6) Precipitated Calcium Carbonate 118.53Ground Calcium Carbonate 9.75 Methyltrimethoxysilane 4.83 Slurry 80%Titanium Ethyl Acetoacetate 20% 2.25 MethyltrimethoxysilaneTetra-n-butoxy titanate 0.84 3-Mercaptopropyltrimethoxysilane 0.33

Amount Speedmixer Component (g) Sample 28 Polydimethylsiloxane 100% endcapped with 163.47 (prophetic) 95% β 5% α di-ethyltrimethoxysilyl groupsPrecipitated Calcium Carbonate 118.53 Ground Calcium Carbonate 9.75Methyltrimethoxysilane 4.83 Slurry 80% Titanium Ethyl Acetoacetate 2.2520% Methyltrimethoxysilane Tetra-n-butoxy titanate 0.843-Mercaptopropyltrimethoxysilane 0.33

Creep Recovery SOT TFT Sample Description (%) (%) (min) (min) Sample 2366.4% β ETM 188.0 39.9 11 30 (comparative) Sample 24 76.6% β ETM 107.410.6 5 25 (comparative) Sample 25 86.8% β ETM 61.9 4.4 13 28(comparative) Sample 26 96.4% β ETM 43.3 3.1 7 22 (practical) Sample 27  65% β EHM 22.4 1.2 1 12 (comparative) Sample 28   95% β EHM 10.9 0.5 05 (practical)

Amount Speedmixer Component (g) Sample 29 Polydimethylsiloxane 100% endcapped with 171.9 66.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 33.6% α ethyltrimethoxy silyl group containingtetra- methyldisiloxane (the ethyltrimethoxysilyl- terminatedtetramethyldisiloxane prepared as in Comparative Example 3) PrecipitatedCalcium Carbonate 108.99 Ground Calcium Carbonate 62.1Methyltrimethoxysilane 7.62 Slurry 80% Titanium Ethyl Acetoacetate 2.7620% Methyltrimethoxysilane Tetra-n-butoxy titanate 1.263-Mercaptopropyltrimethoxysilane 0.87N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.39

Amount Speedmixer Component (g) Sample 30 Polydimethylsiloxane 100% endcapped with 171.9 76.6% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 23.4% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl- terminatedtetramethyldisiloxane used in this sample was a blend prepared from theethyltrimethoxysilyl group containing tetramethyldisiloxanes inComparative Example 3 and Example 1 to achieve the 76.6/23.4 isomerratio) Precipitated Calcium Carbonate 108.99 Ground Calcium Carbonate62.1 Methyltrimethoxysilane 7.62 Slurry 80% Titanium Ethyl Acetoacetate20% 2.76 Methyltrimethoxysilane Tetra-n-butoxy titanate 1.263-Mercaptopropyltrimethoxysilane 0.87N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.39

Amount Speedmixer Component (g) Sample 31 Polydimethylsiloxane 100% endcapped with 171.9 86.8% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 13.2% α ethyltrimethoxy silyl group containingtetra- methyldisiloxane (the ethyltrimethoxysilyl- terminatedtetramethyldisiloxane was a blend prepared from the ethyltrimethoxysilylgroup containing tetramethyldisiloxanes in Comparative Example 3 andExample 1 to achieve 86.8/13.2 isomer ratio) Precipitated CalciumCarbonate 108.99 Ground Calcium Carbonate 62.1 Methyltrimethoxysilane7.62 Slurry 80% Titanium Ethyl Acetoacetate 2.76 20%Methyltrimethoxysilane Tetra-n-butoxy titanate 1.263-Mercaptopropyltrimethoxysilane 0.87N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.39

Amount Speedmixer Component (g) Sample 32 Polydimethylsiloxane 100% endcapped with 171.9 96.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 3.6% α ethyltrimethoxy silyl group containingtetra- methyldisiloxane (the ethyltrimethoxysilyl- terminatedtetramethyldisiloxane prepared as in Example 1) Precipitated CalciumCarbonate 108.99 Ground Calcium Carbonate 62.1 Methyltrimethoxysilane7.62 Slurry 80% Titanium Ethyl Acetoacetate 20% 2.76Methyltrimethoxysilane Tetra-n-butoxy titanate 1.263-Mercaptopropyltrimethoxysilane 0.87N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.39

Amount Speedmixer Component (g) Sample 33 Polydimethylsiloxane 100% endcapped with 171.9 65% β 35% α di-ethyltrimethoxysilyl groups (preparedas in Comparative Example 6) Precipitated Calcium Carbonate 108.99Ground Calcium Carbonate 62.1 Methyltrimethoxysilane 7.62 Slurry 80%Titanium Ethyl Acetoacetate 2.76 20% MethyltrimethoxysilaneTetra-n-butoxy titanate 1.26 3-Mercaptopropyltrimethoxysilane 0.87N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.39

Amount Speedmixer Component (g) Sample 34 Polydimethylsiloxane 100% endcapped with 171.9 (prophetic) 95% β 5% α di-ethyltrimethoxysilyl groupsPrecipitated Calcium Carbonate 108.99 Ground Calcium Carbonate 62.1Methyltrimethoxysilane 7.62 Slurry 80% Titanium Ethyl Acetoacetate 20%2.76 Methyltrimethoxysilane Tetra-n-butoxy titanate 1.263-Mercaptopropyltrimethoxysilane 0.87N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.39

Creep Recovery SOT TFT Sample Description (%) (%) (min) (min) Sample 2966.4% β ETM 1940.3 2358.1 15 41 (comparative) Sample 30 76.6% β ETM192.5 58.5 10 34 (comparative) Sample 31 86.8% β ETM 95.5 11.5 13 30(comparative) Sample 32 96.4% β ETM 98.3 13.7 6 23 (practical) Sample 33  65% β EHM 72.8 6.4 4 17 (comparative) Sample 34   95% β EHM 23 1.4 111 (practical)

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 158.22 ple 35 66.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 33.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Comparative Example 3) PrecipitatedCalcium Carbonate 131.22 Methyltrimethoxysilane 7.26 Slurry 80% TitaniumEthyl Acetoacetate 20% 3.3 Methyltrimethoxysilane

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 76.6% β 158.22 ple 36 ethyltrimethoxysilyl group containingtetramethyldisiloxane and 23.4% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane used in this sample was a blend prepared from theethyltrimethoxysilyl group containing tetramethyldisiloxanes inComparative Example 3 and Example 1 to achieve the 76.6/23.4 isomerratio) Precipitated Calcium Carbonate 131.22 Methyltrimethoxysilane 7.26Slurry 80% Titanium Ethyl Acetoacetate 20% 3.3 Methyltrimethoxysilane

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 86.8% β 158.22 ple 37 ethyltrimethoxysilyl group containingtetramethyldisiloxane and 13.2% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane was a blend prepared from the ethyltrimethoxysilylgroup containing tetramethyldisiloxanes in Comparative Example 3 andExample 1 to achieve 86.8/13.2 isomer ratio) Precipitated CalciumCarbonate 131.22 Methyltrimethoxysilane 7.26 Slurry 80% Titanium EthylAcetoacetate 20% 3.3 Methyltrimethoxysilane

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 96.4% β 158.22 ple 38 ethyltrimethoxysilyl group containingtetramethyldisiloxane and 3.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Example 1) Precipitated CalciumCarbonate 131.22 Methyltrimethoxysilane 7.26 Slurry 80% Titanium EthylAcetoacetate 20% 3.3 Methyltrimethoxysilane

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped 158.22 ple 39 with 65% β 35% α di-ethyltrimethoxysilyl groups(prepared as in Comparative Example 6) Precipitated Calcium Carbonate131.22 Methyltrimethoxysilane 7.26 Slurry 80% Titanium EthylAcetoacetate 3.3 20% Methyltrimethoxysilane

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped 158.22 ple 40 with 95% β 5% α di-ethyltrimethoxysilyl (pro-groups phetic) Precipitated Calcium Carbonate 131.22Methyltrimethoxysilane 7.26 Slurry 80% Titanium Ethyl Acetoacetate 3.320% Methyltrimethoxysilane

Creep Recovery SOT TFT Sample Description (%) (%) (min) (min) Sample 3566.4% β ETM 30.8 2.5 13 19 (comparative) Sample 36 76.6% β ETM 27.4 1.97 16 (comparative) Sample 37 86.8% β ETM 18.0 1.2 11 23 (comparative)Sample 38 96.4% β ETM 14.7 1.0 4 18 (practical) Sample 39   65% β EHM10.8 0.6 2 8 (comparative) Sample 40   95% β EHM 5.8 0.3 0 7 (practical)

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 66.4% β 208.04 ple 41 ethyltrimethoxysilyl group containingtetramethyldisiloxane and 33.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Comparative Example 3) PrecipitatedCalcium Carbonate 126.88 Methyltrimethoxysilane 10.15 Slurry 80%Titanium Ethyl Acetoacetate 20% 4.66 MethyltrimethoxysilaneN-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.28

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 76.6% β 208.04 ple 42 ethyltrimethoxysilyl group containingtetramethyldisiloxane and 23.4% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane used in this sample was a blend prepared from theethyltrimethoxysilyl group containing tetramethyldisiloxanes inComparative Example 3 and Example 1 to achieve the 76.6/23.4 isomerratio) Precipitated Calcium Carbonate 126.88 Methyltrimethoxysilane10.15 Slurry 80% Titanium Ethyl Acetoacetate 20% 4.66Methyltrimethoxysilane N-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.28

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 208.04 ple 43 86.8% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 13.2% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane was a blend prepared from the ethyltrimethoxysilylgroup containing tetramethyldisiloxanes in Comparative Example 3 andExample 1 to achieve 86.8/13.2 isomer ratio) Precipitated CalciumCarbonate 126.88 Methyltrimethoxysilane 10.15 Slurry 80% Titanium EthylAcetoacetate 20% 4.66 MethyltrimethoxysilaneN-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.28

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 208.04 ple 44 96.4% β ethyltrimethoxysilyl group containingtetramethyldisiloxane and 3.6% α ethyltrimethoxy silyl group containingtetramethyldisiloxane (the ethyltrimethoxysilyl-terminatedtetramethyldisiloxane prepared as in Example 1) Precipitated CalciumCarbonate 126.88 Methyltrimethoxysilane 10.15 Slurry 80% Titanium EthylAcetoacetate 20% 4.66 MethyltrimethoxysilaneN-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.28

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 208.04 ple 45 65% β 35% α di-ethyltrimethoxysilyl groups(prepared as in Comparative Example 6) Precipitated Calcium Carbonate126.88 Methyltrimethoxysilane 10.15 Slurry 80% Titanium EthylAcetoacetate 20% 4.66 MethyltrimethoxysilaneN-(3-(Trimethoxysilyl)propyl)ethylenediamine 0.28

Amount Speedmixer Component (g) Sam- Polydimethylsiloxane 100% endcapped with 208.04 ple 46 95% β 5% α di-ethyltrimethoxysilyl (pro-groups phetic) Precipitated Calcium Carbonate 126.88Methyltrimethoxysilane 10.15 Slurry 80% Titanium Ethyl Acetoacetate 4.6620% Methyltrimethoxysilane N-(3-(Trimethoxysilyl)propyl)ethylenediamine0.28

Creep Recovery SOT TFT Sample Description (%) (%) (min) (min) Sample 3566.4% β ETM 58.5 4.1 12 21 (comparative) Sample 36 76.6% β ETM 32.9 2.210 16 (comparative) Sample 37 86.8% β ETM 20.1 1.3 10 17 (comparative)Sample 38 96.4% β ETM 12.9 0.8 6 13 (practical) Sample 39   65% β EHM16.6 0.9 5 10 (comparative) Sample 40   95% β EHM 9 0.4 3 8 (practical)

In this example 47, ethyltrimethoxysilyl tetramethyldisiloxane wasprepared in a round bottom flask was loaded with 25 g of TMDS and astirbar, then capped with an addition funnel containing 20 g of VTMmixed with Ir (0.2 mL of 0.05M Ir solution in toluene, as [Ir(COD)Cl]₂from Strem). Thermocouples were inserted through a septum into the flaskto allow for temperature logging and temperature control. A stream of98% N₂/2%O₂ was bubbled into the VTM and through the rest of theapparatus for 10 min. The flask was preheated to 50° C., and then asteady drip (1 drop/sec) of VTM/catalyst mixture was added. An exothermimmediately began and gradually rose until the temp approached 70° C. Atthis point, the heating mantle was lowered which reduced the insulationof the flask and allowed the temperature to gradually fall. Afterdropping to 64° C. the mantle was returned to the flask and thetemperature began to raise again. After the addition was complete, theset point on the heat controller was raised to 70° C. for 20 min, andthen heating was stopped and the reaction apparatus was cleaned up.

Conversion to Time ethyltrimethoxysilyl conversion to equivalents % VTM(minutes) tetramethyldisiloxane ethyltrimethoxysilane VTM added consumed5 3.2 0.6 0.1 37.5 10 17.5 1 0.25 74.1 15 32.3 1.6 0.4 84.8 20 50 1.90.6 86.5 25 61.9 3.1 0.75 86.6 30 70.1 3.3 0.85 86.4 35 78.8 3.7 0.9586.8 45 88.8 3.9 1 92.7 90 94.7 4.2 1 98.9

Within the 94.7% overall yield of ethyltrimethoxy-tetramethyldisiloxane(ETM converter), 97% were linear ETM converter, 1% was branched ETMconverter, and 2% was a dehydrogenative silylation by-product (whichcontained unsaturation).

INDUSTRIAL APPLICABILITY

The examples and comparative examples above show that when apolyorganosiloxane is endblocked with an alkoxy-functionalorganohydrogensiloxane oligomer prepared by the method described hereinand having >90 mol % of linear divalent hydrocarbon linking groups, andthe resulting endblocked polyorganosiloxane is formulated into acondensation reaction curable composition, the composition cures fasterthan a comparative composition containing a polyorganosiloxaneendblocked with an alkoxy-functional organohydrogensiloxane oligomerhaving a lower amount of linear divalent hydrocarbyl linking groups anda higher amount of branched divalent hydrocarbon linking groups.

1. A method for preparing an alkoxy-functional organohydrogensiloxaneoligomer, where the method comprises: 1) reacting starting materialscomprising: (A) a polyorganohydrogensiloxane oligomer of unit formula:(HR¹ ₂SiO_(1/2))_(e)(R¹³SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R₁SiO_(3/2))_(i)(HSiO_(3/2))_(j)(Si O_(4/2))_(k) wheresubscripts e, f, g, h, i, j, and k have values such that 5≥e≥0, 5≥f≥0,10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or 1, withthe proviso that a quantity (e+g+j)≥2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently a monovalenthydrocarbon group of 1 to 18 carbon or a monovalent halogenatedhydrocarbon group of 1 to 18 carbon atoms; (B) an aliphaticallyunsaturated alkoxysilane of formula:

 where each R² is independently an aliphatically unsaturated monovalenthydrocarbon group of 2 to 18 carbon atoms, each R³ is independently amonovalent hydrocarbon group of 1 to 18 carbon atoms, subscript c is 0or 1; and (C) an iridium complex of formula [Ir(R₅)_(x)(R⁶)_(y)]_(z),where subscript x is 1 or 2, R⁵ is a 1,5-cyclooctadiene ligand or a2,5-norbornadiene ligand, subscript y is 0, 1 or 2, R⁶ is a ligand thatcan be activated at a temperature less than a boiling point of theorganohydrogensiloxane oligomer, and subscript z is 1 or 2, therebypreparing a reaction product comprising the alkoxy-functionalorganohydrogensiloxane oligomer; and optionally 2) isolating thealkoxy-functional organohydrogensiloxane oligomer prepared in step 1).2. The method of claim 1, where (C) the iridium complex is selected fromthe group consisting of: [Ir(I)(1,5-cyclooctadiene)Cl]-dimer; Ir(I)1,5-cyclooctadiene acetyl acetonate;Ir(I)(1,5-cyclooctadiene)₂(tetrakis(3,5-bis(trifluoromethyl)phenyl)borate);[Ir(I)(1,5-cyclooctadiene)(OMe)]-dimer,Ir(I)(1,5-cyclooctadiene)(hexafluoroacetyl acetonate), Ir(I)(1,5-cyclooctadiene)(CH₃CN)₂, Ir(I) (1,5-cyclooctadiene)(pyridine),Ir(I) (1,5-cyclooctadiene)(indenyl), and mixtures thereof.
 3. The methodof claim 1, where the alkoxy-functional organohydrogensiloxane oligomerhas unit formula:

where R¹, R³, and subscripts c, f, h, i, and k are as described above,subscript b is 0 to 2, m>0, and a quantity (m+n+o+p)=(e+g+j), and each Dis independently a divalent hydrocarbon group of 2 to 18 carbon atoms,with the proviso that >90 mol % of all D groups produced in step 1) arelinear.
 4. The method of claim 1, where (A) thepolyorganohydrogensiloxane oligomer has formula:

where subscript a is 0 to
 10. 5. The method of claim 4, where thealkoxy-functional organohydrogensiloxane oligomer has formula:

where D is a divalent hydrocarbon group of 2 to 18 carbon atoms, withthe proviso that >90 mol % of D are linear divalent hydrocarbon groups.6. The method of claim 1, where (A) the polyorganohydrogensiloxaneoligomer has unit formula: (HR¹ ₂SiO_(1/2))₃(R¹₂SiO_(2/2))_(q)(R¹SiO_(3/2)), where subscript q is 0 to
 3. 7. The methodof claim 6, where (A) the polyorganohydrogensiloxane oligomer hasformula:


8. The method of claim 7, where alkoxy-functional organohydrogensiloxaneoligomer has formulae comprising:

or both, where each D is independently a divalent hydrocarbon group of 2to 18 carbon atoms, with the proviso that >90 mol % of D are lineardivalent hydrocarbon groups.
 9. The method of claim 1, where theorganohydrogensiloxane oligomer is a cyclic organohydrogensiloxaneoligomer of unit formula: (R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(s), wheresubscript s≥3 and subscript v≥0.
 10. The method of claim 9, where thealkoxy-functional organohydrogensiloxane oligomer has unit formula:(R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(t)

where subscript t≥0, subscript u≥1, and a quantity (t+u)=s.
 11. A methodfor preparing a poly-alkoxy functional polyorganosiloxane, where themethod comprises: 1) reacting starting materials comprising: (A) apolyorganohydrogensiloxane oligomer of unit formula: HR¹₂SiO_(1/2))_(e)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(Si O_(4/2))_(k) wheresubscripts e, f, g, h, i, j, and k have values such that 5≥e≥0, 5≥f≥0,10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or 1, withthe proviso that a quantity (e+g+j)≥2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently a monovalenthydrocarbon group of 1 to 18 carbon or a monovalent halogenatedhydrocarbon group of 1 to 18 carbon atoms; (B) an aliphaticallyunsaturated alkoxysilane of formula:

 where each R² is independently an aliphatically unsaturated monovalenthydrocarbon group of 2 to 18 carbon atoms, each R³ is independently amonovalent hydrocarbon group of 1 to 18 carbon atoms, subscript c is 0or 1; and (C) an iridium complex of formula [Ir(R⁵)_(x)(R⁶)_(y)]_(z),where subscript x is 1 or 2, R⁵ is a 1,5-cyclooctadiene ligand or a2,5-norbornadiene ligand, subscript y is 0, 1 or 2, R⁶ is a ligand thatcan be activated at a temperature less than a boiling point of theorganohydrogensiloxane oligomer, and subscript z is 1 or 2, therebypreparing a reaction product comprising the alkoxy-functionalorganohydrogensiloxane oligomer; and optionally 2) isolating thealkoxy-functional organohydrogensiloxane oligomer prepared in step 1);3) reacting starting materials comprising: (a) the alkoxy-functionalorganohydrogensiloxane oligomer; (b) a polyorganosiloxane having, permolecule, an average of at least two aliphatically unsaturatedmonovalent hydrocarbon groups; and (c) a hydrosilylation reactioncatalyst.
 12. The method of claim 11, where starting material (b) is apolydiorganosiloxane of formula:

where subscript n is 1 to 2,000.
 13. The method of claim 11, where thepoly-alkoxy functional polyorganosiloxane has formula:

where each D¹ is independently a divalent hydrocarbon group.
 14. Themethod of claim 11, where the poly-alkoxy functional polyorganosiloxanehas formula:

where each D¹ is independently a divalent hydrocarbon group.
 15. Amethod for making a condensation reaction composition comprising: 1)reacting starting materials comprising: (A) a polyorganohydrogensiloxaneoligomer of unit formula: (HR¹ ₂SiO_(1/2))_(e)(R¹₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2)) (Si O_(4/2))_(k) wheresubscripts e, f, g, h, i, j, and k have values such that 5≥e≥0, 5≥f≥0,10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or 1, withthe proviso that a quantity (e+g+j)≥2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently a monovalenthydrocarbon group of 1 to 18 carbon or a monovalent halogenatedhydrocarbon group of 1 to 18 carbon atoms; (B) an aliphaticallyunsaturated alkoxysilane of formula:

 where each R² is independently an aliphatically unsaturated monovalenthydrocarbon group of 2 to 18 carbon atoms, each R³ is independently amonovalent hydrocarbon group of 1 to 18 carbon atoms, subscript c is 0or 1; and (C) an iridium complex of formula [Ir(R⁵)_(x)(R⁶)_(y)]_(z),where subscript x is 1 or 2, R⁵ is a 1,5-cyclooctadiene ligand or a2,5-norbornadiene ligand, subscript y is 0, 1 or 2, R⁶ is a ligand thatcan be activated at a temperature less than a boiling point of theorganohydrogensiloxane oligomer, and subscript z is 1 or 2, therebypreparing a reaction product comprising the alkoxy-functionalorganohydrogensiloxane oligomer; and optionally 2) isolating thealkoxy-functional organohydrogensiloxane oligomer prepared in step 1);3) reacting starting materials comprising: (a) the alkoxy-functionalorganohydrogensiloxane oligomer; (b) a polyorganosiloxane having, permolecule, an average of at least two aliphatically unsaturatedmonovalent hydrocarbon groups; and (c) a hydrosilylation reactioncatalyst; and 4) mixing starting materials comprising (i) thepoly-alkoxy functional polyorganosiloxane, and (ii) a condensationreaction catalyst.
 16. The method of claim 15, where the condensationreaction catalyst comprises a titanate catalyst.
 17. The method of claim16, where the composition further comprises one or more additionalstarting materials, where the one or more additional starting materialsare selected from the group consisting of (iii) a filler; (iv) a fillertreating (v) a crosslinker; (vi) an adhesion promoter, (vii) a dryingagent; (viii) an extender, a plasticizer, or a combination thereof; (ix)a biocide; (x) a flame retardant; (xi) a chain lengthener; (xii) anendblocker; (xiii) a nonreactive binder; (xiv) an anti-aging additive;(xv) a water release agent; (xvi) a pigment; (xvii) a rheologicaladditive; (xviii) a vehicle (such as a solvent and/or a diluent); (xix)a tackifying agent; (xx) a corrosion inhibitor; and a combination of twoor more of (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi),(xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), and (xx).18.-23. (canceled)